NL1012190C2 - Compositions stabilized with dioxopiperazinyl derivatives. - Google Patents

Description

Compositions stabilized with dioxopiperazinyl derivatives - ·, m

The invention relates to compositions based on polyoxymethylene, mixtures of polycarbonate with an acrylonitrile-butadiene-styrene ter-polymer or a functional acrylate resin and a crosslinking agent, which are stabilized by adding a compound of the class 3,3,5,5-tetra-alkyl-piperazine-2,6-dione, on new compounds of this class, on the use of the new compounds as stabilizers for organic matter against the deleterious effects of light, oxygen and / or heat and on stabilized organic matter.

The structure and numbering of 3,3,5,5-tetra-alkylpiperazine-2,6-dione is as shown in the formula: n 5; r

° H

wherein R is alkyl.

The preparation of some of the above compounds, specific derivatives thereof and the use of these compounds as stabilizers, e.g. for polyethylene, polypropylene, nylon or ABS, is shown by T. Yoshioka et al., Bull. Chem. Soc. Jap. 45, 1855-1860 (1972); Luston and Vass, Makromol. Chem., Macromol. Symp. (1989), 27; and in documents US-A-4413096; C.A. 99: 141068; C.A. 96: 25 104 191; US-A-3969316; US-A-3936456; US-A-3928357; US-A-3928330; US-A-3920659; US-A-3919234.

It has now been found that certain compounds of the class of 3,3,5,5-tetra-alkylpiperazine-2,6-dione are extremely suitable as stabilizers for polyoxy-methylene, mixtures of a polycarbonate with an acrylonitrile-butadiene-styrene -30 terpolymer or coatings based on a functional acrylic resin and a cross-linking agent.

The invention therefore relates to a composition comprising 1012190 2

(A) a synthetic organic polymer selected from the group consisting of polyoxymethylene, a mixture of a polycarbonate with an acrylonitrile-butadiene-styrene terpolymer and a coating system based on a functional acrylic resin and a cross-linking agent and 5 (B) as a stabilizer a compound of the formula I or II

FL O

r-N N - A (0 10

L R4 ° J S

15 Z - ^ ^ _px — R · —X - Z,

UN

R, T

R5-N N- (R 9-C) -R 15 20 "tM ° LR / ° J p where p is in the range from 1 to 10; s is in the range from 1 to 8; 25 if s is 1, A is C1-C18 alkyl; C2-C18 alkyl which is substituted with NH2, hydroxy, halogen and / or OR10 or is interrupted by -0-, -NH- and / or -NR10-; or A is C1-C18 alkyl substituted with -COORn or phenyl; when s is 2, 30A is C 2 -C 10 alkylene; C 4 -C 12 alkenylene; C 3 -C 15 alkylene which is substituted with one or more OH and / o 'is interrupted by one or more oxygen, phenylene , C 1 -C 4 alkyl-phenylene, -COO-, -CONH-, 1012190 3

- χγΝγχ ~ V

ν ^ Ν, -ΝΗ- and / or -NRio-; 5 Υ 'ΑΝΛ Ζ Ζ Ν Ζ when s is 3, A is C3-C10 alkane triyl; C3 -C12 alkane triyl which is substituted with ÖH and / or interrupted by oxygen, -NH- or -NR10-; or one of the groups with the formulas (lilac) - (illd) 10 is r! o (llla) o 1 o

Xr · x2 r ^ 15 - (R „-CO) Γ R, s - X γΝ γχ_ R1S - <CO-R2e) - N ^ N (lllb)

- (R9-CO) - r15— X

20

- (R9-CO). R1S

\ - (Rb-CO) - R1S- Ν γ, Χ- R, s - (CO-R28).

; (111c) 25 z ^ 8γ- (Illd) o Xj O Bf X, X2 R9 T012190 4 when s is 4, A C4-C10 alkantetryl; C4 -C12 alkantetryl which is substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; or one of the groups of formulas (IVa) - (lVd) is 15 4 \ Ar4xV llv „

"A

^ 29 20 1 - (Re-C °) r, s ~ x γΝ γ'Χ- R'1S 'χγN y x'R, s ico * Jr ΝγΝ N ^ N (IVb) - (R9-co) - r, 5-X xr, 5- (co-r9) -25 - (Rs-CO) -R15

- (Ra-CO): R1S- N N ^ / X- R15- (CO-R28) .- N ^ N

30 T

XR, 5-tCO-R28) .- (1VC) 1012190 5 - <R9-CO) - R, s R15 <CO-R28) .- - (Re'c °): R, s - N γΝ γ'Ν - R1S - (CO-R28) -

5 NyN

I (IVd) when s is 5, A is C 5 -C 10 alkane pentayl; C5 -C12 alkane pentayl substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; or one of the groups with formulas 10 (Va) - (Vc) is 4γ * ° 0 χΓ 1 / o r /

15 xAr r \ x R

X. X5> f-R30 \ (Va)

L II

RA> ° ™ 29 20 - (R.CO): Β, - * γΝ γ, Χ- FT ,, -XNNR, s- <CO-R,) - ΝγΝ Nv ^ N (Vb) - (R9- CO) —R) S — X XR, s - (CO-R9) - - (R9-CO) —R18 R15 {CO-R8) -

- <fVco> · «is" N γΝ ^ N- R16- (CO-R28) -N ^ N

X-R, s- (CO-R 28) - (Vc) 30 when s is 6, 1012190 6 A C6-C10 alkane hexayl; Ce-Cn alkane hexayl which is substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; or one of the groups with the formulas (Via) - (Vlf) is rL ^ o 5 ° Y u, Λ x ΛγΛ X, χ5γπ30 \ (Via) 0 RA> ° 10. f - (R.-CO), - R „R15 <CO-R29) j- - (R8-CO) - r15 - n ^ n- Rl51CO-R28) - ΝγΝ 15 (R30-CO) .- R15 -N - R, S- (C0-R31) - (Vib) - (Rg-CO) - R, 5 Rl5 <CO-Re) i— - (R8-CO) r Ri5 - N ^ x- R'1s -x N - R, 5 - (CO-Rb) - ΝγΝ Ν'γΝ (Vic) - (Rg-COJj R15 XX— R1S - fC0-R9) - 25 R15 <CO-R8) - - (Ra-CO) r R , b - x ^ X- R'1S -X N'ri5 ^ C0-Re) .-

N .N

- (Re-CO) —R, s — X N-Ri5 - {CO-R9) - (Fld) 30 R, s' 1012190 7 n R ,, <co-Re) - - (R8-CO): R15 / ”'. - y R .__ N-R’rr-X ^ N NR ,, - (CO-Re) - ~ (FVCO): R16-N N X-R15 f 15 T Ί T T νΛν N ^ N (Vie)

c NV I ii T

I z ^ N ^ N-R15- <CO-Re) rz R15 <co-r8) - - (Rg-CO) - R, 5 - XN, .X-R '- N R'ii Χγ N γ x 'R' co-Re) i

10 X. N N ^ N ν 'N

1 Ϊ if 1 (Vlf) - (Rg-CO): R15 — X X | N X-R 2 CO-Rg - X-R 7 <CO-Re) r-R 15 (CO-Rg) - J 5 as 7is, A C 7-C 10 alkane heptayl; C7 -C12 alkane heptayl which is substituted with OH and / or interrupted by oxygen, -NH- or -NR.10-; or one of the groups of formulas (Vila) - (Vlld) is - (R8-CO) -R, R15 (CO-Rg) .— 20 - <R, -CO) f R „- N ^ X- R .is -VNN - R ^ CO-R ^ - (Rg-CO). R16 x N-R15- (CO-R9) - (Vila) R5- (co-r9) - 25 ~ {Re-CO): R15 R1; <CO-Re) .— - (Rg-CO) - RIS - NN ^ x-R'ii -R'ii-Χγ N γ N - R1S fCO-Rg) - ΝγΝ 7 "^ ΝγΝ (Vllb) 2 ZN NR ^ -tCO-Rg) .X — R15 - (C0-R9) - R, s <C0'Re) - 1012 190 8 - (Rb-CO): R, b- XN X-R '~ -N R 'is X γ N γ X' 'ιι ^ Γ 5 Νγ'Ν X Yy * NYN (Vile) - (R8-CO). R15 — XX XR ^ CO-R,) - N ^ R - ((: 0- Re) r r15 <co-r8) .— Rt ·, (('° -rb) - 10 - (Re ~ col: R, 5- x γΧ-R'Ti- ¥ Η' ~ * Χγ Ν · γ X 'R' ^ CO'Re) i— l 'nn ^ m * Vn YXXT (Viid) - (R.-CO) .- R15 — XX ^ NN' Rs-tCO-R.Jj- X- R, T < C0-Re) i- I R15 <c ° -Re) - R15 (co-r8) - 15 when s is 8, A Cjj-C10 alkane octayl; Cs-Cn alkane octayl which is substituted with OH and / or is interrupted by oxygen , -NH- or -NRio-; or one of the groups with the formulas (Villa) - (Vlllb) is - (R8'CO) - R15 R15 <co'r8) - 20 1 \ / - (Rb-CO) rR ^ -N ^ N ^ XR; -XNN - R, 5 fCO-R ^ - ΝγΝ ΝγΝ - (Re-CO) —R1S — N N-R15- (CO-R9) - (Villa) - <R, CO ) rR, (, R, 5 - «= 0-8,) r 25 - (Re-CO): R) 5 R; ilcO-R8) - - (R, -co); Rr ._- 'Ny - Λ — R k— r '! 5 χγ HYNH ”IA f'l <VIMb> 30 - (H -CO): Rls-X-R1S1C0 2ΛΝ N-R, Y R "-ICO.RJ.- R, 5 <COR,) r t01 9, 2190, the index i is zero or 1;

R1, R2, R3 and Rt independently of one another are C1 -C4 alkyl or R1 and R2 or R3 and R4 together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl ring; 5 R5 hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH2CN; C 1 -C 6 alkoxy; C5 -C12 cycloalkoxy; C3 -C8 alkenyl; C3 -C8 alkynyl; C7 -C12 phenylalkyl; C7-C15 phenylalkyl substituted on the phenyl ring with 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; C7-C15 phenylalkoxy; C7-C15 is phenylalkoxy which is substituted on the phenyl ring with 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R5 C 1 -C 6 alkanoyl; C3-C5alke-10 noyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group is -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl;

Rg and R9 and R2g, R29, R30, R31, R32 and R33 are independently C1-C4 alkylene; R 1 C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl, C 7 -C 15 phenylalkyl which is unsubstituted or substituted on the phenyl ring with a moiety selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R10 is C 1 -C 6 alkyl or Q-C 8 alkanoyl substituted with OH,

C 1 -C 12 alkoxy and / or a residue of benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone group are unsubstituted or substituted with OH, halogen, C 1 -C 4 alkyl and / or C 1 -C 6 alkoxy; R11 C 1 -C 18 alkyl; C 2 -C 18 alkyl substituted with NH 2, NHR 10, N (R 10) 2, nitro, hydroxy and / or C 1 -C 6 alkoxy; C3 -C18 alkenyl; C5 -C12 cycloalkyl; C5 -C12 cycloalkyl which is substituted with C1 -C4 alkyl and / or is interrupted by -O-; R12, R13 and R14 independently of each other are C2 -C10 alkylene, C3 -C12 alkylene substituted with OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-; C4 -C12 alkenylene; R15 and R'15 independently of each other C2 -C10 alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-;

R 16 C 3 -C 10 alkanetriyl; C3 -C12 alkantriyl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; 30 Rn C4-C10 alkantetryl; C4 -C12 alkanetetryl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-;

Ris C5-C10 alkane pentayl; C5 -C12 alkane pentayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; 1012190 10

R19 C6 -C10 alkane hexayl; C 1 -C 3 alkane hexayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR 10 -; X is -O-, -NH- or -N (R, O) -;

Xu X2, X3, X4, Xs, X6, X7 and X8 are independently -O- or -NH-; 5 o r 4 \ Y-O- or a radical of the formula N-R - (CO-R 9) (N N 5 js / \ R 1/0 r 2 10 Z represents halogen, NH 2, NHRjo, N (Rio) or C 1 -C 4 alkoxy;

Zi has one of the meanings of Z or is -X-R'15-XH and w

N ^ N

r2 o I

Z2 is H or a radical of the formula /; R5-N N- (R gC) -R 15 20 * 3 ^ 0 'r / o

If a connection contains more than one group displayed with the same symbol, these groups can be the same or different within their defined meanings.

Alkylene, cycloalkylene or alkenylene radicals can be attached to different carbon atoms or to the same carbon atom and thus comprise alkyl idene, cycloalkylidene and alkenylidene, respectively.

All residues may be straight or branched where appropriate, unless otherwise noted. Hetero atoms are non-carbon atoms, such as, for example, N, O, S or P atoms. Alkyl or alkylene interrupted by hetero groups such as oxygen or cycloalkylene may be interrupted by one or more of these groups, as long as no bonds of type 0-0, O-N etc. exist.

1012190 11

The index s is the valence of A; for example, A as alkyl is a monovalent, A as alkylene is a divalent, A as alkantriyl is a trivalent, A as alkane tetryl is a quadivalent, A as alkane pentayl is a pentival, A as alkane hexayl is a hexivalent, A as alkane heptayl is a seven-valent and A as the alkane octayl is a octavalent saturated hydrocarbon residue. The A residue interrupted is interrupted in a single carbon-carbon bond. The A moiety interrupted and / or substituted may be a moiety interrupted in one or more single carbon-carbon bonds by one or more divalent interrupting moieties, a moiety substituted with one or more monovalent substituents, or a moiety that is both interrupted in one or more single carbon-carbon bonds by one or more divalent interrupting groups and is substituted with one or more monovalent substituents.

Thus, examples of A as C3-C15 include alkylene which is substituted with one or more OH and / or is interrupted by oxygen, phenylene, C1-C4 alkylphenylene, -COO, -CONH, -NH or -NR10 groups of the formulas CH2CH (OH) CH2, CH2-C (CH2OH) 2-CH2, (CH2) 2-N (CHO) - (CH2> 2, (CH2> 2-NH- (CH2) 2, (CH2) 2 -0- (CH2> 2, (CH2) 2-0- (CH2) 2-0- (CH2) 2, CH2-C0-0- (CH2) 2-0- (CH2> 2-0-CO-CH2 , CH2 -C0-0- (CH2) 6-0 -C0-CH2, CH2 -C0-0- (CH2) 2-0 -C0-CH2.

Halogen is preferably chlorine or bromine, especially chlorine.

2Q C6 -C12 aryl is preferably phenyl or naphthyl, especially phenyl.

The compounds of the invention may be pure or may be mixtures of compounds.

R 1, R 2, R 3, R 4, R 5, R 10 as alkyl are, within the given definitions, for example methyl, ethyl, propyl such as n- or isopropyl, butyl such as n-, iso-, sec- and tert-butyl, pen-25 tyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

Re, R9, R12, R13, R14, Ru, R'i5 and R2g - R33 as alkylene are, within the given definitions, for example, methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,1-30 butylene, 2,2-butylene , 2,3-butylene or -C5H10-, -C6Hi2-, -C7H14-, -CgHio-, -C9H18-, -C10H20-, -C11H22-, -C12H24-, -C13H26-, -C14H28-, -C15H30- -Ci6H32-, -C17H34-, -Ci8H36-.

Rs, R9 and R28 - R33 are particularly preferred as methylene.

1012190 12

In R-5, Rio, Ru as C5-C12 cycloalkyl or cycloalkoxy, the cycloalkyl portion is, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl. C5-C12 cycloalkenyl includes cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl, cyclopodecenyl.

C 1 -C 4 alkyl or alkoxy substituted cycloalkyl or phenyl (containing mainly 1-3, eg 1 or 2 alkyl groups) includes 2 or 4-methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, methylphenyl, methoxy, among others phenyl, dimethylphenyl.

Phenylalkyl or phenylalkoxy are alkyl or alkoxy each of which is substituted with phenyl. R5, R10 as phenylalkyl or phenylalkoxy are, within the given definitions, for example, benzyl, benzyloxy, α-methylbenzyl, α-methylbenzyloxy, cumyl, cumyloxy.

Rs and R10 as alkanoyl are, for example, formyl, acetyl, propionyl, butyryl, penta-noyi, octanoyl; R5 as alkanoyl is preferably Ct-Cg alkanoyl, especially acetyl.

Alkenoyl radicals, as in the definition of R5, are most preferably acrylic ethyl or methacryloyl.

Alkenyl radicals, as in the definition of R5, are most preferably allyl.

X is preferably NH; Most preferably Xi-Xó are O; Most preferably Z is N (Rio) 2; Most preferably i is zero.

The index p is preferably in the range of 2-6.

A preferred mixture of polycarbonate with an acrylonitrile-butadiene-styrene terpolymer (component (A) of the above composition) is a mixture of 10 to 90 parts by weight of polycarbonate with 90 to 10 parts by weight of acrylonitrile-butadiene-styrene terpolymer. .

Polycarbonates present in these blends are, in particular, those polymers having the following recurring unit

O

- £ -0-W-30, wherein W o is a divalent phenolic radical. Examples of W are given, inter alia, in US-A-4960863 and DE-A-3922496. For example, W can be derived from hydroquinone, resorcinol, dihydroxybiphenylene or bisphenols in the broadest sense of the term such as bis (hydroxyphenyl) alkanes, cycloalkanes, sulfides, ethers, 101219 (1 13 ketones, sulfones, sulfoxides, a, <x'-) bis (hydroxyphenyl) diisopropylbenzenes, for example the compounds 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3.5 -dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-di-bromo-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, or the 5 bisphenols of the formulas \ / \ _ / chT ch> 10 ch3 — J JL.

CH / OHf CH3 / ^ v ^^ XCH3 ch3 - ch3 ch3 J - CH., Ch3 - (- ch3 ch3 CH3 CH2-C (CH3) 3 T012190 14

- · «R

O O ~? H3 ff ^ T ^ 0 \ ^ \ / CH3 5 IsJI ^ Aa Ο — ζ ft \ CH =

^ ^ “A

The composition according to the invention preferably contains as a further component 10 (C) a UV absorber from the class of the benzotriazoles, o-hydroxyphenyl-s-triazines and / or benzophenones, examples of which are listed below.

Preference is given to a composition in which the compound of the formula I (component B) s ranges from 2 to 6; 15 when s is 2, A is C 2 -C 10 alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; or a group of the formula -R.8-COO-R12-OCO-R9- (11a); if s is 3, 20 A is a group with the formula (lilac)

Rl O (llla) oio V ^ XrRif V — X2 ^ 25 when s is 4, A is one of the groups of formulas (IVa) or (IVd) 10121901 15 * 28ν ^ -® 5 0 Xj o

Re I ^ 9 (IVa)) \ Λ Λ * 29 10 "(Rg-COJj R1S R15 <C0-R28) - - (R8-co) - r15 - n ^ / N- r15 ^ co-r28) -

N ^ N

I (IVd) 15 z when s is 5, A is a group of the formula 20 rI ^ o

28V ^ O

xl! χΛτ "γΓ R 'X <Χ5γΗ30 \ (Va) 25 rX * ° ° π29 if s is 6, A is one of the groups with formulas (VIb) - (Vlf) T012190 16 - (R9-CO) - R, 5 R <CO-Rm): - \ / - (R8-CO) - R1S- N Rts- (CO-R28) .-

N ^ N

5 (R3o'CO) γ R15 ~ N— R, j ^ CO-Rj,) - (Vlb) _ (R (j "CO) - R) 5 R15 <CO-Rb) - - (Re-CO) r R, s- N γΝ ^ x- R-15-ΧγΝ ^ Ν - R1S- (CO-R,) - 10 ΝγΝ (vic) - (Rg-CO) - R, 5— X x — R1S - (CO- Rg) - 15 R15 <C0-Re> f- - (Re-CO): R, 5-X ^ N ^ x- R'1S - XNN - R1S iCO-Rg) .—

N ^ N

- (R9-CO). R15 X N-R1S - (CO-Rg) - (Fld) R1S (CO-Rg).

20 - (R '-CO); R15 R15 (CO-Rglj 25 - (Re-CO) - R1 & - N ^ x — R'ii —- Ij * R, ü χγ Ν γ Ν R. ^ co-Re) - Ν ν Ν ^ Ν (Vie) Ζ Ζ ^ Ν NR ^ CO-Rg) - Ζ R15 <C0-Ra> - 1012190 5 17

- (R, CO); R '- X N vX-IR'-Y-NYγ NY X

IVN n "I? NYN (VIO

5 - (R> .co ,, R, 5-i X-R ^ cor,) -

Rt5 <c ° -Re) r the index i is zero or 1;

R 1, R 2, R 3 and R 4 are independently methyl; R R hydrogen; C 1 -C 18 alkyl; oxyl; OH; C 1 -C 6 alkoxy; C5-C12 cycloalkoxy; C3 -C8 is alkenyl; or R5 C 1 -C 6 alkanoyl; C3-C5alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group is -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl;

Ru and R9 and R28, R29, R30, R31, R32 and R33 are independently methylene;

R 10 is C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl; R12 C2-C10 alkylene; or C3-C12alkylene interrupted by oxygen is -NH- or -NR10-;

Ru and R 15 are independently C 2 -C 10 alkylene;

Rn is C4-C10 alkantetryl;

Ris is C5-C10 alkane pentayl; X is -O-, -NH- or -N (RIO) -;

Xi, X2, X3, X4, X5, Xe, X7 and X8 are independently -O- or -NH-; and Z represents NHR10, N (R, o) 2 or C1 -C4 alkoxy.

Many compounds of the above component B are new. The invention therefore also relates to a compound of the formula (Γ) or (II) 'r-ML.

r / ° J s 30 T012190 18 z, - [f ^ —x — R'ü x * 2

5 N \ ^ N

π, ^ Η ° T

R5-H ^ “(Rg ^ fRis * 3-M 0

K o J

10 where p is in the range of 1-10; s is in the range of 1 to 8, preferably 2 to 8;

R 1, R 2, R 3, and R 4 are independently C 1 -C 4 alkyl; R5 hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH2CN; C 1 -C 18 alkoxy; C5-C12 cycloalkoxy; C3-15 C alkenyl; C3 -C8 alkynyl; C7-C12 phenylalkyl; C7-C15 phenylalkyl substituted on the phenyl ring with 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; C7 -C15 phenylalkoxy; C7-C15 is phenylalkoxy which is substituted on the phenyl ring with 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R5 C 1 -C 6 alkanoyl; C3-C5alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl; when s is 1, A is C 2 -C 18 alkylene substituted with OR30, where R30 is C 1 -C 6 alkyl or C 1 -C 6 alkanoyl substituted with a benzophenonyl or benzophenonyloxy radical, wherein one or both phenyl rings of the benzophenone group are unsubstituted are or are substituted with OH, halogen, C1 -C4 alkyl and / or C1 -C18 alkoxy; When s is 2, A is C 3 -C 15 alkylene which is substituted with one or more OH and / or is interrupted by one or more oxygen, phenylene, C 1 -C 4 alkyl phenylene, -COO-, -CONH-, z

N ^ N

30 X _X ^ N ^ X -

N v N

ΛΑ

Z N Z

-NH- and / or -NR10-; or A is C4 -C12 alkenylene; 1012190 19 and when R 1 is not hydrogen, A also C 2 -C 10 alkylene; C2 -C10 alkylene interrupted by phenylene or C1 -C4 alkylphenylene; when s is 3, A is C 3 -C 10 alkanetriyl; C3 -C12 alkantriyl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups with the formulas (Illa) - (llld) rIo (lila)

O I O

. Λ ^ Λ /

10 R8 ^ XrR15 R-ig-χΓ RT

- (R8-CO) - R? S - X ^ X "R.s-tCO-R ^) - N <yN (lllb)

15 - (R.-CO) .— R15— X

"(Rg'CO). R, s \ - (R8-CO) - R1S- N γΝ ^ X- R15iCO-R28) -20 \ (Hlc) rI * o 28y (llld) 25 o * jo 30 when s is 4, A C4-C10 alkantetryl ; C 4 -C 12 alkanetetryl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups with formulas (IVa) - (IVd) ΤΌ12190 20 I ** ^ 28 \ | £? · 0 Ο Χ | Re - 5 Re χι I X2 R® (IVa) X.

Λ R £ i 10 - (R8-CO) - Rl5- x γΝ γΧ ~ R'16 'X γ N γ XRis- <CO-R8) i— ΝγΝ N ^ N (| Vb) - (R9-CO ) - r15 — xx — R1S - (CO-R9) - 15 - (R9-CO) - Π ,, \ - (Rg-CO) r R1S- N γΝ γΧ "Rts-tCO- ^ i ΝγΝ \ (> Vc ) X- R15- (CO-R 28) r 20 - (Rg-CO) - R, s R, 5 <CO-R28) r - (Rg-CO) - R15-N γΝ γΝ-R15-iCO-R28 ) -

N ^ N

T (IVd) 25 z when s is 5, 30 A C 5 -C 10 alkane pentayl; C5 -C12 alkane pentayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR] O-; or is one of the groups with formulas (Va) - (Vc) 101219 ° 21 rL'v ^ ° o 5 χI / 1 ηΙ / Χ2 R9 8 k SrR-- {Va)

i4 I

> 0 ”29 10 1 R, 5 <co-rb) - - (FVCO): R, s- X γΝ γΧ“ R \ 5 'Χγ N γ N' Rs ΝγΝ N ^ N (Vb) 15 - (R „ -CO) - r16— X xr, 6 - (CO-R9) - - (R9-CO) - R, s Rl5 <C0-Ra) j · - - (R8-CO) - R, s- N γ, 15- R151CO-R28) .-

20 T

(Vc) X-R15- (CO-R28) - when s is 6, 25 A C6-C10 alkane hexayl; C6 -C12 alkane hexayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups with the formulas (Via) - (Vlf) 101219® 22 RLy- ° o 5. X ίΛ / 1/2 9 (custard) Ο Λο ° (¾ 10 - (Re-C0) - R, s R15 <CO-Rm) - - (Rg-CO) r R15 - NN ^ N ~ R15- (CO -R28) .- ΝγΝ 15 I (Vlb) (R30-CO) rR15-NR, ^ CO-R3l) r> - (RB-CO) -R ,,, R15 <CO_Re) j - CVCO): R, b - N ^ X- R'15 -Χγ N - R ^ CO-R ,,) - 20 N ^ NN ^ .N (Vic) (RlJ-CO) j — R ,,, XX “" Rt;> (CO -Ru) .- - 25 R15 <C ° -R8) - - (R8-CO): R15 - x ^ X- R'15 -x N - R1S - (CO-R8) .-

ΝγΝ N ^ N

- (Rg-CO). R15 X N-R15 - (CO-Re) .— (Fld) 30 r15- (CO-R9) - '1012190 23 - (R8-CO) -. R15 ^, 5 <C °' Re) i - (R .-CO): R, s- N ^ ^ XYNYN 'R, ^ CO'Re) i_ 5 II nYn (vie)

Y l ji T

ZAN n-r ^ co-r,) - Z

R15 (c ° -Ra) r 10 - | R, -CO); R, rXYNyX ~ R'r-J ^ XYNYX, gCWVr nv'n n "n ΝγΝ (Vlf) - (R.-CO): R154 x Vx * η * »*> Γ X" R15 <c ° -Re) r 15 when s is 7, A C7-C10 alkane heptayl; C7 -C12 alkane heptayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups with the formulas (Vila) - (Vlld) 20 "(IVCO): ^, Rlb (CO-RB) r- (IVCO): H ,, - N ^ x- R '^ - Χγ NN Ri :, iCO-Re) -

N ^ N N ^ N

(R., - CO). R,. -X N-R, .. (COR ,,). (Vila).

R.g-fCO-R ,,).

25 - (Re-CO): R15 R, gco-RB) - - (RB-CO): Rlb-N NX — R'— N R'ii Χγ ^ ^ · «“ gCO-RJ- ^ Τ Ι ^ < V [.b) 30 XZ ^ N ^ NR, gCO-R8) - X— R, 5- (CO-R9) - R) 5tc ° -Ru) r 1012190 '24 -: R "- XV VX-R— Ï - ^ \ "YX 'KC0'R,) i ~ l VN" "N NY" (VHC) 5 - (R..C0) .- R, SX xAnXx-R, s- (C0-r,) - N ^ R, t <co.r ,, - R15 <co-r8) .- R «<cwyi - (R.-CO): R, - Xx — R — N R'ïl Χγ NY X M '" 10 l J. n ^ nn ^ n VL ji T (VI Id) - (rb-co) r -Ï χΛΝΛΝ · Β, ^ ω · Ρι) Γ XR ^ coig- 1 "R ^ iCO-R,) - R15 ( CO-RB) r 15 when s is 8, A is C 1 -C 10 alkane octayl; C 1 -C 12 alkane octayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR 10 -; or one of the groups is with the formulas (Villa) - (Vlllb) - (R | fCO). Rl R, 5 <co-r8) - 20 - (R. CO): R,., - N ^, χ- R ') 5 -X N- Rl54CO-Re) - - (lt, i-CO) j Rii, —N N- R, s - (CO-Ry) - (villa) - (R ^ -CO) .— R) b R15 (C ° -Rg) | 25 - (Rj-CO): R R15 tc ° 'R8) j I «D! - (R8-CO) - R, s - NN ^ / X-R '—— N R'ii Χγ NYN' R'S - <co-Re) i— TN ν 'n (Vlllb) γ Ϊ if 1 30 - ( R-CO) -R-X 2 (NR, S 4 CO-Re) - X-R, b - (CO-R 9) -101219® 25 the index i is zero or 1;

Re and R9 and R28, R29, R30, R31, R32 and R33 are independently methylene, and when R5 is not hydrogen, additionally include ethylene; R10 is C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl, C 7 -C 15 phenylalkyl unsubstituted or substituted on the phenyl ring with a moiety selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; R12, R13 and R14 independently of each other C2-C10alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-; C4 -C12 alkenylene; R15 and R'15 independently of each other C2-C10alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-;

R 16 C 3 -C 10 alkanetriyl; C3 -C12 alkane triyl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; Rn C4-C10 alkantetryl; C 4 -C 12 alkanetetryl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-;

Ris C5-C10 alkane pentayl; C5 -C12 alkane pentayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; R19 C10 -C10 alkane hexayl; C6 -C12 alkane hexayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; X is -O-, -NH- or -N (R, O) -;

Xi, X2, X3, X4, X5, X6 are independently -O- or -NH-;

Ov FC

25 y (r 3 Y -O- or a radical of the formula N-R r WCO-R q). N is N-Rc; / 'Mr, r 2 represents 30 Z halogen, NH 2, NHR 10, N (Rio) 2 or C 1 -C 4 alkoxy;

Zi has one of the meanings of Z or is -X-R'is-XH and 1012190 '26 \ Μ.

Z Pres

5 N \ ^ N

Z2 H or a radical of the formula R2, p | is; "r-M /

R5-N N- (R S-C) rR, B

Rs-4— (° r / 0 10

Preferred meanings in formula (Γ) include those, if appropriate, given above for formula (1).

Also preferred is a compound of formula (Γ) or (11) wherein p is in the range of 2-6, s is in the range of 2 to 8; R 1, R 2, R 3 and R 4 are independently of each other methyl or ethyl;

Rs hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH2CN; C 1 -C 18 alkoxy; C5-C12 cycloalkoxy; C3 -C8 alkenyl; C7-C12 phenylalkyl; C7-C15 is phenylalkoxy; or R5 C 1 -C 6 alkanoyl; C3-C5alkenoyl; C1 -C18 alkanoyloxy; glycidyl; or a group is -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl; When s is 2, A is C3-C12alkylene substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; C4-C12alkenylene; or one of the groups of formulas (11a) - (11e) is "-Re-COO-Rie-OCO-FV; -R8-CONH-R, 3-NHCO-Ra-; -R8-COO-R14-NHCO-R8-; dia) m <"°> (Η» -00): Β, ΓΧγΝγΖ N ^ N (member)

30 - (Ry-CO) -R, b-X

1012190 27 - (Ra-CCO3 — R, s - (B3-CO} fR1s-NyN ^ z 5 (,, e) z and when R5 is not hydrogen, A also C2-C10 alkylene; C2-C10 alkylene which is interrupted by phenylene or C1 -C4 alkylphenylene; 10 when s is 3, A is C3-C10 alkane triyl; or one of the groups of formulas (Ilia) - (Hid) is rI, 0

ir OIO

Re XrR15 R '? T ~ X2 R9 - (R8-CO) r R, 5 - X ^ X- Rl51CO-R2e) .- 20 ΝγΝ (mb)

- (R9-CO) —R, g — X - (Re-CO) —RJS

25 - (Rg-CO) - R, 5 - N X- R1S iCO-R28) .- ΝγΝ z (MIC) 1012190 28 j (Hid) 5 0- X | 0 v. R ^ Jl / R (r ^ xr X2 when s is 4, A C4-C10 alkaneetryl; or one of the groups of formulas (IVa) - (IVd) is 10 x |

0 I 9 15 ^ A

FL ^ Xf "X2 R9 6 'x (IVa) Λ 20 - OVCO): R,; - xR-) 5 -x X - R, 5iCO-Re) - ΝγΝ (IVb) (R ^ -CO) j R15 XXR s (CO-Ra).

25 - (RJ-CO) - R, b - (R „-CO) - Htb - NN ^ X - R15- (CO-R28) - ΝγΝ X ~ R, b" (C0-R2g) - (IVc) 30 1 101219® 29 - (R9-co) - ri5 R15 <co-r28) - - (Re-CO): R1S- NR ^ CO-R, *) .-

5 N ^ N

T (| Vd) when s is 5, A C5-C10 alkane pentayl; or is a group of formula (Va)

10 I

X3 ο ^ / Λ2 n9 "8 \ x r (Va)

* f XsY

15 R / ° ° ^ 29 when s is 6, A Ce-Cjo alkane hexayl; or one of the groups of formulas (Vlb) - (Vlf) is 20 - (R9-CO) - R, 3 Ri5tCO-RZ9) r - '(R8-CO): R1S- NN - fl15 - (CO-R28 ) - ΝγΝ 25 (Rg ^ oj-R ^ -NR ^ co-Rg,) .- (Vlb) - (Rb-CO) -R1s R, 5 <co-r8) - - (Re-CO) r R1S - N ^ x- R'15 -χ N - R1S ^ CO-Rg) - 30 Νγ-Ν Ννγ> Ν (Vic) - (Rg-CO) j Rlb XX — R1S - (CO-R9) - 1012190 30 R15 < c ° -RJr / 5 '(Hh-CO) 7 R ,,, - X γΝ ^ X ~ R'15 - Χγ N γ N' ^ 3CO-R6) i

ΝγΝ N ^ N

(R, ico) | ........ R ,, ..... x N-nls- (co-fgr (vw> R, b '~ (C0 Ry); 10 r15 <00- ^ 4— - (FL-CO): R ,, / 1 \ _R · --XN ^, NRls <CO-Ra) j -ανοο.ι -.- ΗγΗ ^ -ΡΓ .- ΎΥ <Vte> N VN 1> 1 '

1 Z ^ N ^ NRR151C0-Re) - Z

.5 Ri5 ^ CO'Re) r ___ ____ Xv / Ns / XR ^ C ° -R ») r

- (Η8-00}: Βι5-Χ ^ Ν ^ Χ-R'1S V 15 Y Y

T ^ T n ^ n Νγ, (Vlf),. co | .R _X x- ^ NXx. ,, ii <Co.R,) r x-R.rWr

Risk when s is 7, A is C7-C10 alkaneheptayl; when s is 8, 25 A CVC10 alkane octayl; whether one of the groups of the formulas is (Villa) - (VUIb); the index i is zero or 1;

Rk and Ry and R28, R29, R29, R31, R32 and R33 are independently methylene;

R10 is C1 -C4 alkyl, C1 -C10 alkanoyl, C5 -C12 cycloalkyl, C7 -C15 phenylalkyl; R12, R13 and Rh are independently C2-C10 alkylene; C3-C12alkylene which is substituted with OH and / or interrupted by oxygen, -NH- or -NR | (r; C4-C12alkenylene; roi 2190 31

Ris and R'u independently of each other are C 2 -C 10 alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-;

R 16 is C 3 -C 10 alkanetriyl; R 1 is C 4 -C 10 alkantetryl;

Ris is C5-C10 alkane pentayl; X is -O-, -NH- or -N (R10> -;

Xi, X2, X3, X4, X5 are independently -O- or -NH-; and Z represents halogen, NH2, NHR10, N (Rio) 2 or C1 -C4 alkoxy.

Especially preferred is a compound of the formula (Γ) wherein s is in the range 2 to 6;

R1, R2, R3 and R4 are independently methyl or ethyl;

R 5 is hydrogen, C 1 -C 18 alkyl; oxyl; OH; CH2CN; C 1 -C 6 alkoxy; C5-C12 cycloalkoxy; C3 -C8 alkenyl; C7-C12 phenylalkyl; C7-C15 is phenylalkoxy; or R5 C 1 -C 6 alkanoyl; C3-C5alke-15 noyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group is -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl; when s is 2, A is C3-C12alkylene substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; C4-C12alkenylene; or a group of the formula (Ha) is 20 -R8-COO-R12-OCO-R9-; (na) and when R5 is not hydrogen, A also includes C2-C10 alkylene; when s is 3, A is C 3 -C 10 alkanetriyl; or one of the groups of formulas is (lilac), (Hlb) or (Illd); when s is 4, 25 A is C4-C10 alkantetryl; or is one of the groups of formulas (IVa), (IVb) or (IVd); when s is 5, A is C5-C10 alkane pentayl; when s is 6, A is one of the groups of formulas (VIb) - (Vlf); 30 the index i is zero or 1;

Rg and R9 and R28, R29, R30, R31, R32 and R33 are independently methylene; R10 is C1 -C6 alkyl, C1 -C5 alkanoyl, C5 -C12 cycloalkyl; T012190 32

R 12 C 2 -C 10 alkylene; C3 -C12 alkylene which is substituted with OH and / or is interrupted by oxygen is -NH- or -NR10-; R15 and R'15 are independently C2-C10 alkylene; R16 is C3-C10 alkantriyl; R17 is C4-C10 alkantetryl; X is -O-, -NH- or -N (Rio) -;

X 1, X 2, X 3, X »are independently -O- or -NH-; and Z represents NHR10 or N (Rh>) 2.

Most preferred is a compound of the formula (Γ) wherein s is 2, 3, 4 or 6;

R1, R2, R3 and R4 are methyl; R5 hydrogen; C 1 -C 8 alkyl; C 1 -C 18 alkoxy; cyclohexyloxy; allyl; benzyl; acetyl; C3 -C4 alkenoyl; glycidyl; when s is 2, 15 A is C3-C10alkylene substituted with OH or interrupted by oxygen, -NH- or -NR10-; or a group of the formula -R8-COO-R12-OCO-R9- (Ila); and when R 5 is not hydrogen, A also includes C 2 -C 10 alkylene; when s is 3, A is a group of the formula (lila); when s is 4, A is a group of the formula (IVa) or (IVd); When s is 6, A is a group of the formula (Vie); the index i is zero;

R5 and R9 and R28, R29, R30, R31, R32 and R33 are methylene;

R10 is C1 -C8 alkyl, formyl, acetyl or cyclohexyl; R12 C2-C10 alkylene; or C3-C10alkylene interrupted by oxygen; R15 and R'is independently of one another are C 2 -C 10 alkylene; R17 is C4-C10 alkantetryl; X is -NH-;

X 1, X 2, X 3, X »-O-; and Z means N (R10) 2.

The preparation of compounds of the formula I or Γ can start from the compound 3,3,5,5-tetra-alkylpiperazine-2,6-dione and can follow processes described in the documents cited on page 1 or standard methods described in textbooks for organic chemistry or analogous thereto are performed T012190 33; examples of such processes are alkylation, esterification, re-. esterification or etherification, substitution, etc.

Compounds thus obtained can be further derivatized using appropriate synthetic methods known in the art, e.g. analogous to the methods described in EP-A-375612, US-A-5204473, US-A-5004770 and Kummada et al., J. Polym. Sci., Poly. Chem. Ed. 23, 1477 (1985), as well as US 5449776, Example 8, and publications cited therein, for the modification of piperidine derivatives.

The new compounds of the present invention can advantageously be used to stabilize organic matter against the deleterious effect of light, oxygen and / or heat. They are characterized by good compatibility with the substrate and good persistence in the substrate.

Examples of materials to be stabilized according to the invention are: 1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloalkenes, such as for example of cyclopentene or norborome; further polyethylene (which may optionally be cross-linked), for example high density polyethylene (HDPE), high density polyethylene, high molecular weight (HDPE-HMW), high density polyethylene and ultra high molecular weight (HDPE-UHMW), 20 medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, ie the polymers of monoolefins shown in the previous paragraph, in particular polyethylene and polypropylene, can be prepared by various, and in particular the following, processes: a) radical polymerization (usually under high pressure and at increased temperature).

b) by means of a catalyst, the catalyst usually containing one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl groups and / or aryl groups, which may have either n or σ coordination. These metal complexes can be in the free form or they can be fixed on supports, such as, for example, on activated magnesium chloride, titanium (m) chloride, 1012 190 34 aluminum oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts may be active as such in the polymerization or further activating agents may be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, these metal elements being of groups Ia, Ha and / or lilac of the Periodic table. The activators can be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), Metallocene, or Single-Site (SSC) catalysts.

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different kinds of polyethylene (for example LDPE / HDPE).

3. Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as, for example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / butylene 1 copolymers, propylene / sobutylene copolymers, ethylene / butene 1 copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / 20 heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) with ethylene and terpolymers propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norborne; further mixtures of such copolymers with each other and with polymers mentioned under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or statistically constructed polyolefin / carbon monoxide copolymers and mixing thereof with other polymers such as, for example, polyamides.

Hydrocarbon resins (e.g. C5-C9), including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyolefins and starch.

5. Polystyrene, poly (p-methylstyrene), poly (or -methylstyrene).

T012190 35 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate and methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate ; high impact blends of styrene copolymers and another polymer such as, for example, a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butene / styrene or styrene / ethylene / propylene / styrene.

7. Graft copolymers of styrene or α-methylstyrene, such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates resp. Alkyl methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers mentioned under 6), which are known for example as ABS, MBS, ASA or AES polymers .

8. Halogen-containing polymers, such as, for example, polychloroprene, chlorinated rubbers, the chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, such as, for example, poly-vinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

9. Polymers derived from α, β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates; butyl acrylate-modified polymethyl methacrylates, polyacrylamides and polyacrylonitriles.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, such as, for example, acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate-101219® 36 copolymers or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, 5-benzoate, maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with the olefins mentioned under 1).

12. Homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals, such as polyoxymethylene and those polyoxymethylenes, containing co-monomers, such as, for example, ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters and polybutadienes, on the one hand, and aliphatic or aromatic polyisocyanates, on the other, and their precursors.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from amino carboxylic acids or the corresponding lactams, such as polyamide-4, polyamide-6, polyamide-6/6, -6/10, -6/9, - 6/12, -4/6, -12/12, polyamide-11, polyamide-12, aromatic polyamides starting from m-xylene, diamine and adipic acid; polyamides prepared from hexamethylenediamine and iso and / or terephthalic acid and optionally an elastomer as a modifier, for example poly-2,4,4-trimethylhexa-methylene terephthalamide or poly-m-phenylene isophthalamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Further polyamides or copolyamides modified with EPDM or ABS; as well as condensed polyamides ("RIM polyamide systems") during processing.

17. Polyurea, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxy carboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, 1012 190 37 as well as block polyether esters derived from polyethers with hydroxyl end groups; further polyesters modified with polycarbonates or MBS.

19. Polycarbonates and Polyester Carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Cross-linked polymers derived from aldehydes on the one hand and phenols, urea or melamines on the other, such as phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as cross-linking agents, as well as their low-flammability halogen-containing modifications.

24. Crosslinkable acrylic resins derived from substituted acrylic acid esters, such as, for example, from epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins cross-linked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example, products of diglycidyl ethers of bisphenol-A and bisphenol-F, which are cross-linked with conventional curing agents, such as, for example, anhydrides or amines, with or without accelerators.

27. Natural polymers, such as cellulose, natural rubber, gelatin and chemically modified homologous derivatives thereof, such as cellulose acetates, propionates and butyrates, respectively. the cellulose ethers, such as methyl cellulose; as well as natural resins and their derivatives.

28. Blends (polyblends) of the aforementioned polymers, such as, for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTB / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylics, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylic, POM / MBS, PPO / HIPS, PPO / PA

30 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

The invention therefore also provides compositions comprising A) an organic material sensitive to oxidative, thermal and / or actinic degradation and 1012190 38 B) at least one compound of the formula Γ, and provides the use of compounds of the formula Γ for stabilizing organic matter against oxidative, thermal or actinic degradation.

The effects of degradation can include discoloration or molecular degradation or build-up. The invention thus also includes a method of stabilizing organic material against thermal, oxidative and / or actinic degradation / build-up, which comprises applying or adding to this material at least one compound of the formula..

In general, the compounds of the formula I or worden in amounts of from 0.1 to 10%, preferably 0.01 to 5%, in particular 0.01 to 2% (based on the material to be stabilized), added to the material to be stabilized. The use of the new compounds in amounts of 0.05 to 1.5%, in particular 0.1 to 0.5%, is particularly preferred.

In addition to the compounds of the formula I or Γ, the new compositions may comprise as an additional component C one or more conventional additives, such as, for example, those shown below.

1. Antioxidants 1.1 Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-20 tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2 6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methyl-cyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyl-phenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonyl phenols , such as e.g. 2,6-Dinonyl-4-methylphenol, 2,4-dimethyl-6- (1-methylundec-r-yl) -25 phenol, 2,4-dimethyl-6- (1-methylheptadec-l'-yl ) phenol, 2,4-dimethyl-6- (1-methyltridec-1-yl) phenol and mixtures thereof.

1.2 Alkylthiomethylphenols. for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didode-cylthiomethyl-4-nonylphenol.

30 1.3 Hydroquinones and alkolated hydroquinones. for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6 -di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydro-xyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate 1012190 39 bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4 Tocopherols. for example, α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5 Hydroxylated thiodiphenyl ethers. for example 2,2'-thiobis (6-tert-butyl-4-5-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis (2,6-dimethyl) -4-hydroxyphenyl) disulfide.

1.6 Alkvlidene bisphenols. for example 2,2'-methylene bis (6-tert-butyl-4-methyl-phenol), 2,2'-methylene bis (6-tert-butyl-4-ethylphenol), 2,2'-methylene bis [4-methyl- 6- (a-10-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'- methylene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (6-tert-butyl-4-isobutylphenol) 2,2'-Methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-Methylenebis [6- (α, α-dimethyl-benzyl) -4-nonylphenol], 4,4'- methylene bis (2,6-di-tert-butylphenol), 4,4'-methylene bis (6-15 tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2- methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl ) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-do-decyl mercaptobutane, ethylene glycol bis [3,3-bis (3 '-tert-butyl-4) 1-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-20-buty 1,2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3 , 5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5- tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7 O, N and S-benzyl compounds. for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert -butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

30 1.8 Hydroxylated malonates. for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl-benzyl) malonate, didodecyl mercaptoethyl- 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3.5 di-tert-butyl-4-hydroxy-1012 190 40 benzyl) malonate.

1.9 Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di- tert-butyl-4-hydroxy-benzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

5 1.10 Triazine compounds. for example 2,4-bis (octyl mercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5- di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxy-phenoxy) -1, 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3.5-tris (3,5-di-tert -butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5- di-tert-butyl-4-hydroxyphenyl-ethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-buty 1-4-hydroxyphenylpropiony l) hexahydro- 1.3 5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11 Benzyl phosphonates. for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the Ca salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12 Acylaminophenols. e.g. 4-hydroxylauric anilide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic octyl ester.

1.13 Esters of p- (3,5-di-tert-butyl-4-hydroxylphenylpropionic acid) with mono- or polyhydric alcohols, such as eg with methanol, ethanol, n-octanol, iso-octanol, octa-decanol, 1,6- hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N, bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecide Nol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.14 Esters of p-r5-tert-butyl-4-hydroxyl-3-methylphenylpropionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, n-octanol, iso-octanol, octa-decanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl-30 glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaunde decanol, 3-thiapentadecanol, trimethyl hexanediol, trimethylol propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2. 2] octane.

1012190 41 1.15 Esters of β- (3,5-dicvclohexvl-4-hvdroxvfenvOpropionic acid with mono- or polyhydric alcohols, such as eg with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2 -propanediol, neopentyl glycol, thio-diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, lSP-bis (hydroxyethyl) oxalic acid diamide, 3-thiauned decanol, 3-thiapentadecano, trimethylol propane -1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.16 Esters of 3.5-di-tert-butyl-4-hydroxylphenyllazic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N ' bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.

1.17 Amides of B- (3,5-di-tert-butyl-4-hydroxylphenylpropionic acid. Such as e.g.

N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, Ν, ΙΝΓ-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N ' bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N ^ -bisP-p - [3,5-di-tert-butyl-4-hydroxy-phenyl] propionyloxy) ethyl] oxamide (Naugard ® XL-1, supplied by Uniroyal).

1.18 Ascorbic acid (Vitamin C).

1.19 Amine antioxidants. such as e.g. N, N'-diisopropyl-p-phenylenediamine, Ν, Ν1-di-sec-butyl-p-phenylenediamine, N, -bisC 1,4-dimethylpentyl) -p-phenylenediamine, NjN'-bisil-ethyl-S-methylpenty -p-phenylenediamine, N, 1Sr-bis (1-methylheptyl) -p-phenylenediamine, N.N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N ' -di (naphthyl-2) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1 -methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di -sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphlylamine, N-phenyl-2- naphthylamine, octylated diphenylamine, e.g. p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoyl-aminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-methoxy-phenyl) amine, 2,6-di -tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenyl-1012190 42 methane, 4,4-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenyl-methane, 1,2 -di [(2-methylphenyl) amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) -biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthyl amine, mixture of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixture of mono- and di-alkylated nonyldiphenylamines, mixture of mono and dialkylated dodecyldiphenylamines, mixture of mono and di-alkylated isopropyl / isohexyldiphenylamines, mixture of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono and di-alkylated tert-butyl / tert-octylphenothiazines, mixture of mono- and di-alkylated e tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidine-4 -yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol .

2, UV absorbers and light protectants 15 2.1 2-f2, -Hydroxenfenbenzotriazoles- such as, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3,5,5-di-tert-) butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1, 1,3,3-tetramethylbutyl) -phenyl ) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-20-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- ( 3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3, -tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) -phenyl) -5-chloro-benzotriazole, 2- (3, tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl ] -2, -hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxy-25-carbonylethyl) phenyl) -5-chloro-benzotriazole, 2 - (3'-tert-butyl-2'-hydroxy-5 - (2-methoxy-carbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonyl-ethyl) phenyl) benzotriazole, 2- (3'-tert- butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2, hydroxy-5, -methylphenyl) benzotriazole, 2- (3'-tert -butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-30 methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benztriazol-2-ylphenol]; the transesterification product of 2- [3 '-tert-butyl-5' - (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzo-triazole with polyethylene glycol 300; [R-CH2CH2-COO-CH2CH2] 2- with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '- (a α-dimethyl-benzyl-benzyl) -5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- [2'-Hydroxy-3 - (1,1,3,3-tetramethylbutyl) -5 '- (oi, α-dimethylbenzyl) phenyl] benzotriazole.

2.2 2-hydroxybenzophenone etL such as, for example, the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4-trihydroxy, 2'- hydroxy-4,4'-dimethoxy derivative.

2.3 Esters of optionally substituted benzoic acids. such as, for example, 4-tert-butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert- butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid -2-methyl-4,6-di-tert-butylphenyl ester.

2.4 Acrvaten. such as, for example, ocyan-P, P-diphenylacrylic acid ethyl ester resp. isooctyl ester, α-carbomethoxy-cinnamic acid methyl ester, α-cyano-P-methyl-p-methoxy-cinnamic acid methyl ester, respectively. -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

2.5 Nickel compounds, such as, for example, nickel complexes of 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyl dithiocarbamate, nickel salts of the monoalkyl esters, eg the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl- 5-hydroxypyrazole, optionally with additional ligands.

2.6 Sterically hindered amines. such as, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, n-butyl-3,5-di-tert-butyl- 4-hydroxybenzylmalonic acid bis (1,2,6,6,6-pentamethyl-4-piperidyl) ester, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hy -droxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3, 5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 butanetetracarboxylate, 1,1 '- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2 2,6,6-tetramethylpiperidine, bis (1,2,6,6,6-pentamethylpiperidyl) -2-n-bu-1012190 44 tyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetra methyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6, 6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 5 4-morpholino-2,6-dichloro-1,3 , 5-triazine, the condensation product of 2-chloro-4,6-di (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3 -aminopropylamino) ethane, the condensation product of 2-chloro-4,6-di (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2 bis (3-aminopropylamino) ethane> 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1 -10 (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,6,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearylloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N, N'-bis (2,2,6,6- tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexy lamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine, as well as 4 butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,6,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2- undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl -1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- ( 4-methoxyphenyl) ethylene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, diester of 4-methoxymethylene malonic acid with 1,2,2, 6,6-pentamethyl-4-hydroxypiperidin, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, reaction product of maleic anhydride-a olefin copolymer with 2,2,6,6-tetramethyl-4-25 aminopiperidine or 1,2,6,6,6-pentamethyl-4-aminopiperidine.

2.7 Oxalic acid diamides. such as, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di- tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, 1Sr-bis (3-dimethylaminopropyl) -oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and the mixture thereof with 2-ethoxy-30 2-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy as well as o- and p-ethoxy-di-substituted oxanilides.

2.8 2- (2-Hydroxyphenyl-V 1,3,5-triazines. Such as, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) ) -4,6-bis (2,4-dimethyl-101 2190 45 phenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy -4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl ) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxypheny I) -5 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2 -hydroxy-3-octyl-oxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tri-decyloxy-2-hydroxypropoxy) - 2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6 bis (2,4-dimethyl-10-phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-dipheny 11, 3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3 -butoxy- 2-hydroxypropoxy) phenyl] -1,3-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2 -hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] -phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

15 3. Metal deactivators. such as, for example, Ν, Ν'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, 1Sr-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) ) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isoflaloyl dihydrazide, sebacoyl bisphenyl hydrazide, Ν, Ν1-diacetyladipoyldihydrazide, N, N'-bis (N-salicyloxy) oxaly -20 oyl) thiopropionyl dihydrazide.

4. Phosphites and Phosphonites. such as, for example, triphenylphosphite, diphenylalkylphosphites, phenyl dialkylphosphites, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite (2,4-butylphenylphenyl) phosphite) butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6 -tris (tert-butylphenyl) -pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl- 12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3, 2-dioxa-phosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl-methylphosphite, 2,2, 2 "-nitrilo [triethyltris (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3.3', 5.5 1-tetra-tert-butyl-1,1-biphenyl-2,2'-diyl) phosphite.

The following phosphites are particularly preferred: 1012190! 46

Tris (2,4-di-tert-butylphenyl) phosphite (lrgafos® 168, Ciba-Geigy), tris (nonylphenyl) phosphite, Γ (CH2), C. ^ / C (CH => = yC γ, 5 fAv H3C-CH PFF ° CH2CH2 N (B) (V xx ° \ (CH3) 3C ^ X ^ \ / ^ / ^ C (CH3) 3 C (CH3) 3 (CH; i)., CL 3 10 V-o-CH 2 CH (C4 H 9) CH 2 CH 3

O

15 (CH3) 3C

C (CH3) 3 (cH3) 3c- ^ oP; oXo; pop ^ c, oH3) 3 (d) 20 C (CH3) 3 (ch3) 3c C (CH3) 3 (ch3) 3c h> c “C ^ o_p'DC (E) 25 o — 7 '—oy = ^ (E)

C (CH3) 3 (CH3) 3C

10121901 47 Γ CH3 π H3C-c-CH3 P ~~ \ / ~ ° '/ O-p-och2ch3 5, f, v ^ h5cx / y H3C VCH3 3 —I 2 (G) 10 5. Hydroxylamines. such as, for example, Ν, Ν-dibenzylhydroxylamine, Ν, Ν-diethylhydroxylamine, Ν, Ν-dioctylhydroxylamine, Ν, Ν-dilaurylhydroxylamine, Ν, Ν-ditetradecylhydroxylamine, hydrox -decylhydroxylamine, Ν, Ν -dhexadecylhydroxylamine N-octadecylhydroxylamine, N-heptadecyl-N-octadecyl-hydroxylamine, Ν, Ν-dialkylhydroxylamine from hydrogenated tallow fatty amines.

15 6, Nitrons. such as, for example, N-benzyl-alpha-phenyl nitron, N-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptyl nitron, N-lauryl-alpha-undecyl nitron, N-tetradecyl-alpha-tri-decyl nitron, N-hexadecyl alpha pentadecyl nitron, N-octadecyl alpha heptadecyl nitron, N hexadecyl alpha heptadecyl nitron, N octadecyl alpha pentadecyl nitron, N heptadecyl alpha heptadecy 1 nitron, N-octadecyl alfa-hexitronyl alpha of 20 Ν, Ν-dialkylhydroxylamine prepared from hydrogenated tallow fatty amine.

7. Thio servants. such as, for example, thiodipropionic acid dilauryl ester or thiodipropionic acid distearyl ester.

8. Peroxide-destroying compounds, such as esters of β-thiodi-propionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl ditio carbamate, dioctadecyl disulfide pentaerythritol-tetrak is (p-dodecy 1 mercapto) propionate.

9. Stabilizers for polyamide, such as, for example, copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

30 10. Basic co-stabilizers. such as, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate ricinoleate and K-1012190 '48 palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

11. Germinating agents, such as, for example, inorganic substances, such as e.g. talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids, as well as the salts thereof, such as e.g. 4-tert-butyl benzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymers, such as e.g. ionic copolymers ("ionomers").

12. Fillers and reinforcing agents, such as, for example, calcium carbonate, silicates, glass fibers, glass balls, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers .

13. Other additives, such as, for example, plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, reducing agents, optical brighteners, flame retardants, anti-static agents and blowing agents.

15 14. Benzoiuranones resp. indolinones. such as those described in US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7- di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4-20 [2- hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) - 5,7-di-tert-butylbenzophiiran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzoforan-2-one, 3- (3,4-dimethylphenyl ) -5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzophiiran-2-one.

The usual additives are usually used in amounts of. 0.1-10% by weight, for example 0.2-5% by weight, based on the material to be stabilized.

Cost stabilizers which may optionally be added to the stabilizer mixture of the invention are preferably further light stabilizers, such as, for example, those from the class of 2-hydroxyphenyl benzotriazoles, 2-hydroxyphenyl triazines, benzophenones or oxalanilides, e.g. are described in EP-A-453396, EP-A-434608, US-A-5298067, WO 94/18278, GB-A-2297091 and WO 96/28431, and / or further sterically hindered amines derived from 2, 2,6,6-tetraalkylpiperidine containing at least one group of the formula 1012190 49 Ο-ΟΗ ,, ί * - - x x G-CH / CH 3, where G is hydrogen or methyl, especially hydrogen; examples of tetraalkylpiperidine derivatives that can be used as costabilizers with mixtures of the invention are given in EP-A-356677, pages 3-17, sections a) to f). These sections of this EP-A are considered part of the present description.

2-hydroxyphenylbenz triazoles and / or 2-hydroxyphenyl triazines are particularly preferred as cost stabilizers.

Of particular interest is the use of compounds of the formula Γ as stabilizers in synthetic organic polymers, in particular thermoplastic polymers, and corresponding compositions, in film-forming binders for coatings and in reprographic material.

The organic materials to be protected are preferably natural, semisynthetic or preferably synthetic organic materials. Particular preference is given to synthetic organic polymers or mixtures of such polymers, in particular thermoplastic polymers such as polyolefins, in particular polyethylene and polypropylene (PP), and coating compositions. Of particular interest are also polycarbonates and mixtures thereof, for example the polymers listed above at 19 and 28.

The incorporation into the materials can be effected, for example, by mixing in or applying the compounds of the formula Γ and, if desired, further additives according to the methods customary in the prior art. When it comes to polymers, especially synthetic polymers, the incorporation can take place before or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. A further possibility for incorporating the compounds 1012190) 50 of the formula Γ into polymers is to add them before, during or immediately after the polymerization of

-. «I

add the relevant monomers or before cross-linking. In this context, the compound of the formula I can be added as such or otherwise in encapsulated form (e.g. in waxes, oils or polymers). In the case of the addition before or during the polymerization, the compounds of the formula kunnen can also act as a regulator of the chain length of the polymers (chain terminator).

The compounds of the formula Γ can also be added in the form of a masterbatch containing the compound in a concentration of, for example, 2.5 to 25% by weight, relative to the polymers to be stabilized.

The compounds of the formula I or geschikt can be suitably incorporated by the following methods: - as an emulsion or dispersion (eg with latices or emulsion polymers), as a dry mixture during the mixing in of additional components or polymer mixtures, - by add directly to processing equipment (eg extruders, internal mixers, etc.), - as solution or melt.

The new polymer compositions can be used in various forms and / or processed into different products, such as, for example, (up to) films, fibers, tapes, molding compositions, profiles, or as binders for coating materials, adhesives or putty.

Other materials to be stabilized according to the invention are recording materials. By such materials is meant, for example, those described in Re-25 Search Disclosure 1990, 31429 (pages 474-480) for photographic reproduction and other reprographic techniques.

The new recording materials include, for example, those for pressure sensitive copying systems, microcapsule photocopying systems, heat sensitive copying systems, photographic material and inkjet printing.

The new photographic material may be black and white or color photographic material; color photography material is preferred. Further details regarding the structure of color photography material, and the components usable in the new material, may be found, inter alia, in US-A-5538840, column 27, line 25, to column 106. , line 16, and the

-. «I

cited publications; these paragraphs of US-A-5538840 are hereby incorporated by insertion. The use of the new stabilizers of the formula Γ is essentially as described in this reference for UV absorbers or sterically hindered amine stabilizers. Further important components, in particular couplers, are described in US 5578437.

Likewise, of particular interest is the use of the new mixtures comprising the compounds of formula (I) as stabilizers for coatings, for example, for paint. The invention therefore also relates to that composition, the component of which (A) is a film-forming binder for coatings.

The new coating composition preferably comprises 0.01-10 parts by weight (B), in particular 0.05-1% by weight parts (B), more in particular 0.1-5 parts by weight (B), per 100 parts by weight of solid binder (A ).

Multi-layer systems are also possible here, where the concentration of the new stabilizer (component (B)) in the outer layer can be relatively high, for example 1 to 15 parts by weight (B), in particular 3-10 parts by weight (B), per 100 parts by weight of solid binder (A).

The use of the compounds of the formula I or Γ in coatings is accompanied by the additional advantage of preventing delamination, i.e., flaking of the coating from the substrate. This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates.

The binder (component (A)) may in principle be any binder common in industry, such as, for example, those described in Ull-25 Mann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol A18, pp. 368-426, VCH , Weinheim 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, mainly on a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenol, melamine, epoxy and polyurethane resins and mixtures thereof.

Component (A) can be a cold setting or hot setting binder; the addition of a curing catalyst can be beneficial. Suitable catalysts that accelerate binder hardening are described, for example, in Ullmann's Encyclo-1012190 52 Media of Industrial Chemistry, Vol. Al 8, biz. 469, VCH Verlagsgesellschaft, Weinheim

.... «I

1991, described.

Preference is given to coating compositions in which component (A) is a binder comprising a functional acrylic resin and a cross-linking agent.

Examples of coating compositions containing specific binders are: 1. paint based on hot or cold cross-linkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, optionally with addition of a curing catalyst; 2. two-component polyurethane paint based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 3. One-component polyurethane paint based on blocked isocyanates, isocyanurates or polyisocyanates, the blocking being removed during baking, optionally with the addition of a melamine resin; 4. one-component polyurethane paint based on a trisalkoxycarbonyl-triazine cross-linking agent and a hydroxyl-containing resin such as acrylate, polyester or polyether resins; 5. One-component polyurethane paint based on aliphatic or aromatic urethane acrylates or polyurethane acrylates with free amino groups in the urethane structure and melamine resins or polyether resins, if necessary with a curing catalyst; 6. two-component paint based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 7. two-component paint based on (poly) ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester; 8. two-component paint based on carboxyl or amino containing polyacrylates and polyepoxides; 9. Two-component paint based on acrylate resins containing anhydride groups and on a polyhydroxy or polyamino component; 1012190! 53 10. two-component paint based on acrylate-containing anhydrides and polyepoxy skins; 11. two-component paint based on (poly) oxazolines and acrylate resins containing anhydride groups, or unsaturated acrylate resins, or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 12. two-component paint based on unsaturated polyacrylates and polymalonates; 13. Thermoplastic polyacrylate paint based on thermoplastic acrylate resins or externally cross-linking acrylic resins in combination with etherified melamine resins; 10. paint systems based on siloxane-modified or fluorine-modified acrylic resins; 15. paint systems, especially for clearcoats, based on malonate-blocked isocyanates with melamine resins (e.g. hexamethoxymethylamine) as a cross-linking agent (acid-catalyzed); 16. under UV-curing systems based on oligomeric urethane acrylates, or oligomeric urethane acrylates in combination with other oligomers or monomers; Two-step curing systems, which are first cured by heat and then by UV or electron radiation, or vice versa, and the 20 components of which contain ethylenic double bonds which can react upon irradiation with UV light in the presence of a photoinitiator or with an electron beam.

In addition to components (A) and (B), the coating composition according to the invention preferably comprises as component (C) a known light stabilizer of the type of the sterically hindered amines, of the 2- (2-hydroxyphenyl) -1,3,5 triazines and / or the 2-hydroxyphenyl-2H-benzotriazoles, as explained above, examples being listed in 2.1, 2.6 and 2.8 above. Further examples of light stabilizers of the 2- (2-hydroxyphenyl) -1,3,5-triazines type which can be advantageously added can e.g. are found in publications US-A-4619956, EP-A-434608, US-A-5198498, US-A-5322868, US-A-5369140, US-30 A-5298067, WO-94/18278, EP- A-704437, GB-A-2297091, WO-96/28431. Of particular technical importance is the addition of the 2- (2-hydroxyphenyl) -1,3,5-triazines and / or 2-hydroxyphenyl-2H-benzotriazoles, in particular the 2- (2-hydroxyphenyl) -1, 3,5-triazines.

1012190 54

Component (C) is preferably used in an amount of 0.05-5 parts by weight per 100 parts by weight of the solid binder.

Examples of tetraalkylpiperidine derivatives which may advantageously be used as coatings (C) in coatings are given in EP-A-356677, pages 5 sides 3-17, sections a) to f). this EP-A is considered part of the present description. It is particularly advantageous to use the following tetraalkylpiperidine derivatives: bis (2,2,6,6-tetramethylpiperide-4-yl) succinate, bis (2,2,6,6-tetramethylpiperide-4-yl) sebacate, 10 bis (1,2,6,6,6-pentamethylpiperide-4-yl) sebacate, di (1,2,6,6,6-pentamethylpiperide-4-yl) -butyl- (3,5-di -tert-butyl-4-hydroxybenzyl) -malonate, bis (1-octyloxy-2,2,6,6-tetramethylpiperide-4-yl) sebacate, tetra (2,2,6,6-tetramethylpiperide-4-yl) -butane-1,2,3,4-tetracarboxylate, 15 tetra (1,2,6,6,6-pentamethylpiperide-4-yl) -butane-1,2,3,4-tetracarboxylate, 2,2,4 4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro [5.1.11.2] heneicosan, 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9 -tetramethylspiro [4.5] decane-2,4-dione, 1,1-bis (1,2,6,6,6-pentamethylpiperidin-4-yl-oxycarbonyl) -2- (4-methoxyphenyl) ethylene, or a connection with formulas 20 T012190 55

R R

-.11 R-NH- (CH2) 3- N - (CH2) 2- n - (CH2) 3-nh-r ch3 ch3 C4fH9

N- (NH

where R - III '\ CH3 ΝγΝ ch3 n-c4h9 h3CJ ^ \ CH3 1 CH, ch3 R R ch3 15 N - (CH2) f N- (CH2) 2- N - (CH2) 3- N v

R R

f · "· β <" ·

Yr— 20 N γΝ CH3 where R = N-C4H9 °f ° Hj CH, 25 3 i "s 8 VA" --C-CH2-CH2-C-0-CH2-CH2 — NV — o H3C CH, m 30 3 1012190! 56 CH-CH3

I 3 I

HN-C-CH3-C-CH3 I I 2 I 3 5 Γ N ^ N CH3 CH3 --- U, Λ — N- (CH2) 6-N--.

N

fjLCH3 ^ cJ ^ JLch, h'cTnA> NH ch3 pill 3 * 3 3 10 3 0

N ^ N

--yy-N- (CH2) 6-N--

N

r ^ CH3 H3cJ ^ JLCH3 H3C-fNH <cH> NH ^ ch CH3 CHa CH3 CHa 20 25 -η --N - (CH2) 6-N--, I_ JL m 0t lVCH3 H3C4T XCH3

HaC Γ'ΝΗ ^ 'NH CH

CH3 CH; j CH; j 3 where m is 5-50.

1012190 57

In addition to components (A), (B) and, if used, (C), the coating

__ «I

composition also include further components such as, for example, solvents, pigments, dyes, plasticizers, stabilizers, thixotropics, drying catalysts and / or leveling agents. Examples of possible components are those described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Vol A18, pp. 429-471, VCH, Weinheim 1991.

Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, amino-containing resins and / or phosphines. Examples of organometallic compounds are metal carboxylates, in particular those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, in particular those of the metals Al, Ti or Zr, or organometallic compounds such as, for example, organotin compounds.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, the octatates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding linoleates, resinates or phthalates.

Examples of metal chelates are the aluminum, titanium or zircon chelates of acetylacetone, ethyl acetyl acetate, salicyl aldehyde, salicyl aldoxime, o-hydroxyacetophene or ethyl trifluoroacetylacetate, and the alkoxides of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.

Examples of amines are, in particular, tertiary amines, for example tributylamine, triethanolamine, N-methyl diethanolamine, N-dimethylethanolamine, N-ethyl morpholine, N-methyl morpholine or diazabicyclooctane (triethylenediamine) and their salts. Further examples are quaternary ammonium salts, for example trimethylbenzylammonium chloride.

Amino-containing resins are a binder and curing catalyst at the same time. Examples thereof are amino-containing acrylate copolymers.

The curing catalyst used can also be a phosphine, for example triphenylphosphine.

The new coating compositions may also be radiation-curable coating compositions. In this case, the binder mainly comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds, which are cured after application by actinic radiation, i.e., are converted into a high molecular weight crosslinked form. When the system is UV curable, it generally also contains a photoinitiator. Relevant systems are described in the above-referenced publication Ullmann's Encyclopedia of Industrial Chemistry, fifth edition, Vol. Al8, pages 451-453. In radiation curable coating compositions, the new stabilizers can be used without the addition of sterically hindered amines.

The coating compositions of the invention can be applied to any desired substrate, such as, for example, to metal, wood, plastic or ceramic materials. They are preferably used as a top coat in the finishing of auto-mobiles. If the topcoat layer comprises two layers, the bottom layer of which is pigmented and the top layer is not pigmented, the new coating composition can be used for either the top or bottom layer or for both layers, but preferably for the top layer.

The new coating compositions can be applied to the substrates by conventional methods, for example, by painting, spraying, pouring, dipping or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, fifth edition, Vol. Al 8, pp. 491-500.

Depending on the binder system, the coatings can be cured at room temperature or by heating. The coatings are preferably cured at 50-20 150 ° C, and in the case of powder coatings or coil coatings even at higher temperatures.

The coatings obtained according to the invention have excellent resistance to the harmful effects of light, oxygen and heat; the good light stability and weather resistance of the coatings thus obtained, for example paint, should in particular be mentioned.

The invention therefore also relates to a coating, in particular paint, which is stabilized against the deleterious effects of light, oxygen and heat by a content of the compound of the formula (I) according to the invention. The paint is preferably a top coat for cars. The invention further relates to a method of stabilizing a coating based on organic polymers against light, oxygen and / or heat damage, which comprises mixing with the coating composition a mixture comprising a compound of the formula (I ) comprises, and to the use of mixtures comprising a compound of the formula (I) 101 2190! 59 in coating compositions include as stabilizers against damage from light, oxygen and / or heat.

The coating composition can include an organic solvent or mixture of solvents in which the binder is soluble. The coating composition can further be an aqueous solution or dispersion. The medium can also be a mixture of an organic solvent and water. The coating composition may be a high solids paint or may be solvent free (e.g., a powder coating material). Powder coatings are, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, fifth edition, A18, pages 438-444. The powder coating material can also be in the form of a peoder suspension (dispersion of the powder in preferably water).

The pigments can be inorganic, organic or metallic pigments. The new coating compositions preferably do not contain pigments and are used as a clear coat.

Likewise, the use of the coating composition as a top coat for automotive applications, especially as a pigmented or unpigmented top coat for paint finishes, is preferred. However, its use with underlying coatings is also possible.

The invention is further illustrated in the examples below. All 20 parts and percentages in the examples and throughout the description and in the claims are, unless otherwise stated, parts by weight and percentages by weight. Room temperature, unless otherwise stated, indicates a temperature in the range of 20-30 ° C. Data for the elemental analysis are in wt%, calculated (ber) or experimentally measured (exp) for the elements C, H and N. In the examples, the following abbreviations are used: wt% by weight; % w / v weight percent by volume; x% (w / v) means x g solid dissolved in 100 ml of liquid; mp. melting point or range; 30 PC polycarbonate; AB S acrylonitrile butadiene styrene terpolymer; POM polyoxymethylene; PP polypropylene; 101 2190 '60 LDPE low density polyethylene; DSC differential scanning calorimetry; NMR nuclear magnetic resonance (from H, unless shown otherwise).

5 A: PREPARATION EXAMPLES

Example A1: Precursor compound 3,3,5,5-tetra-alkylpiperazine-2,6-dione of the formula

10 H

15 / H is obtained according to T. Yoshioka et al., Bull. Chem. Soc. Jap. 45, 1855-1860 (1972); mp. 240-242 ° C.

Example A2: In a 1 L three-necked flask equipped with a stirrer, a thermometer, a condenser drying tube and a gas supply tube, 94 g of 3,3,5,5-tetraalkylpiperazine-2,6- dion (product of example A1) and 57 g of potassium tert-butoxide 25 in 400 ml of dimethylacetamide. The reaction is slightly exothermic and the temperature rises to 55 ° C; 77 g of ethyl bromoacetate are added dropwise to the stirred solution and the mixture is stirred for an additional 5 hours. The reaction mixture is cooled to room temperature and after adding 200 ml CH2Cl2 it is poured into 200 ml water. The organic layer is separated and concentrated under reduced pressure. The residue is dissolved in toluene, filtered and evaporated under reduced pressure. The product of the formula 101219® 5 61 CHg - HN N - s is obtained.

h3c <Lh o o c2h5 o 10 as a white residue; mp. 58-60 ° C.

Example A3: The product of Example A2 is added to a 1 L three-necked flask equipped with a stirrer, a thermometer, a condenser drying tube and a gas supply tube, with 18 g of p-formaldehyde in 120 ml of tert-amyl alcohol and to the reaction mixture, which is heated to 75 ° C, is added dropwise a solution of 24 g of formic acid in 100 ml of tert-amyl alcohol. The reaction mixture is heated to 85 ° C and held at that temperature for 6 hours and then cooled to room temperature. A solution of 21 g of NaOH in 50 ml of water is added. The organic layer is extracted with CH2CI2, washed with water and evaporated under reduced pressure. The product of the formula CH, ^ 25 H'c-vfy ° is collected as a white powder. Melting point: 59 ° C (according to DSC) 30 1012190 62

Example A4: 5 CH, _u h3c-V ύ-οη3

O ^ N ^ O

Y.

10 / λ, CH, o o <? Ha H> G_NW Λ ^ ο-c__c — o— ^ Γ ^ Λ0 15 0γΝγ ° η> 0Ύ ^ ηΛ ° Η '

H3C

The product of Example A3 is added to a 1 L three-necked flask, which.

is equipped with a stirrer, a thermometer, a condensing drying tube and a gas supply tube, with 10 g of pentaerythritol in a solution of 120 ml of xylene. 1 g of lithium amide is added to the solution stirred at 100 ° C. The reaction mixture is slowly heated to 135 ° C and held at this temperature for 24 hours, then cooled to room temperature and filtered and evaporated under reduced pressure. The residue is crystallized from hot n-hexane to give the above product as a white solid with a melting range of 240-244 ° C. Elemental analysis calculated C = 57.0%; H = 7.4%, N = 10.8% measured C = 57.2%, H - 7.3%, N = 10.7% 30 T012190

Example A8: 63 ^ Η, _0_0 / y ^ CH3 5 H3C_Nv n- \, o H2 V-n n-ch3 ^ ÏS> ~ Τ% «H;»,

In a three-necked flask equipped with a stirrer, a thermometer, a condensation drying tube and a gas supply tube, 94 g of 3,3,5,5-tetraalkylpiperazin-2,6-dione and 57 g of potassium tert-butoxide in 400 ml of dimethylacetamide. The mixture is heated to 55 ° C and 77 g of ethyl bromoacetate are added dropwise with stirring and allowed to react for an additional 5 hours, then cooled to 25 ° C. With stirring, a 200 ml portion of CH 2 Cl 2 and a portion of 200 ml water are added to the mixture and the organic layer is collected, dried over Na 2 SO 4 and co-agitated with 400 ml xylene and 22.8 g diethylene glycol in a round bottom flask, which is equipped with a stirrer, a thermometer, a condensing drying tube and a gas supply tube. The solution is heated to reflux temperature and 0.2 g of dibutyltin oxide is added to the mixture and allowed to react for 12 hours, then cooled to 25 ° C. The solution is then concentrated in vacuo and the resulting solid is placed in a round bottom flask equipped with a stirrer, a thermometer, a condenser drying tube and a gas supply tube. 350 ml of tert-amyl alcohol and 28 g of paraformaldehyde are also introduced into the flask and the resulting mixture is heated to 75 ° C and 38.5 g of formic acid are added dropwise with stirring and the reaction is allowed to proceed for 3 hours, the temperature being 75 ° C is held, after which it is cooled to 25 ° C. 1400 ml of CH 2 Cl 2 and 42.7 g of a solution of 50% NaOH in water are added to the mixture with stirring and this is allowed to react for 1 hour at 40 ° C, after which it is cooled to 25 ° C. A portion of 2000 ml of water and 1400 ml of ethyl acetate are added to the mixture and the organic layer is separated, dried over Na2S (> 4 and concentrated in vacuo. The title product is obtained as a white powder, mp 59 ° C (DSC).

101219®

Example A13: 64 H »cT ^ ° yj> ns H.C-V H (CHz) g N N — CH3

In a three-necked flask equipped with a stirrer, a thermometer, a condensation drying tube and a gas supply tube, 100 g of 3,3,5,5-tetraalkylpipera-10-zine-2,6-dione and 66 g of potassium tert-butoxide in 500 ml of Ν, Ν-dimethylacetamide. The mixture is heated to 55 ° C and 68.3 g of 1,6-dibromohexane is added dropwise with stirring and allowed to react for an additional 5 hours, then cooled to 25 ° C. A 200 ml portion of CH 2 Cl 2 and 200 ml of water are added to the mixture with stirring and the organic layer is collected, dried over 15 Na 2 SC> 4 and evaporated under reduced pressure. The resulting solid is then placed together with 600 ml of tert-amyl alcohol and 52 g of paraformaldehyde in a round bottom flask equipped with a stirrer, a thermometer, a condenser drying tube and a gas supply tube. The mixture is heated to 75 ° C and 78 g of formic acid is added dropwise with stirring and allowed to react for 3 hours while keeping the temperature at 75 ° C, then cooling to 25 ° C. 2000 ml of CH 2 Cl 2 and 74 g of a solution of 50% NaOH in water are added to the mixture with stirring and this is allowed to react for 1 hour at 40 ° C, after which it is cooled to 25 ° C. A portion of 3000 ml of water and 2000 ml of ethyl acetate are added to the mixture, the organic layer is separated, dried over Na2SC> 4 and concentrated in vacuo. The title product is obtained as a white powder with a mp. of 94 ° C (DSC).

Example A24: In a three-necked flask equipped with a stirrer, a thermometer and a condenser, 80 ml of Ν, Ν-dimethylacetamide, 42 g of 3,3,5,5-30 tetraalkylpiperazine-2,6-dione and 29 g of potassium tert-butoxide. The mixture is heated to 40 ° C with stirring and then a solution of 19 g of N, N-bis (2-chloroethyl) formamide in 15 ml of Ν, Ν-dimethylacetamide is slowly added dropwise, keeping the temperature below 80 ° C , and this is left to react for 1012 190 65 3 hours. The reaction mixture is cooled to 20 ° C, 150 ml of dichloromethane and 120 ml of water are added with stirring, the organic layer is collected, washed with another 20 ml of water and concentrated in vacuo. A white solid of the formula 5 Λ -½ is obtained.

CH. CHa 10 3 mp. 137-139 ° C.

Example A25: The product of Example A24 is added to a flask equipped with a thermometer and condenser, dissolved in 120 ml of 37% aqueous HCl, heated at reflux temperature and allowed to react for 3 hours. The mixture is then concentrated in vacuo, the resulting solid is suspended in 400 ml of dichloromethane and a 20% aqueous solution of NaOH is added with stirring until the aqueous layer is neutral. The organic layer 20 is collected, dried over sodium sulfate and concentrated in vacuo to give a white solid of the formula

H

u _ U CH3 25 H3C> r ^ N ^ ^ ^ CH3 CH3 CH3 30 mp. 102-104 "C.

10121901

Example A1 7: 66 tn 5

H * C \ W CH

h3c ~ V ν ^ 3η Q S ^ 10 / NV / NX Y U ^ CH3 h9c / γγΛ / \

HC? Y VY

^ 0 ^ 3CH "HN N - '3> y \ is HaC 0 vy HYhYc ^

H = C Η V

A 20.5 g portion of the product of Example A25 is added dropwise over a 30 min period to a three-necked flask provided with a stirrer, a thermometer and a condenser containing 100 ml of CH2 Cl2 and 9.2 g of cyanuric chloride cooled to 5 ° C and allowed to react for 3 hours. A solution of 2 g of NaOH in 8 ml of water is added to the reaction mixture and allowed to warm to room temperature.

With stirring, another 20.5 g portion of the compound is added to the solution, it is heated at reflux for 2 hours, cooled to 25 ° C, 10 g of K2CO3 is added to the reaction mixture, again at reflux for 3 hours heated and cooled to 20 ° C. 200 ml of xylene, 10 g of K2CO3 and 7.7 g of C, Ν-cyclohexylbutylamine are then added to the reaction mixture and this is heated under stirring at 142 ° C for 16 hours, cooled to 20 ° C, washed with 120 ml of water and the organic layer. Evaporation of the solvent under vacuum yields the title product as a white solid with a mp. from 64-66 C.

101 219 »67

Example A21: R-NH- (CH2) 6-N (R) - (CH2) 6-NH-R 5 with R is H 3 C-V S-CH,

Cr'N'TJ

, ο? Λ ιΝ «· ΛίΥ ^ Γ>

V

An 80 g portion of the product of Example A25 is added dropwise over 30 minutes to a three-necked flask equipped with a stirrer, a thermometer and a condenser containing 360 ml of CH2 Cl2 and 36 g of cyanuric chloride, cooled to 5 ° C and this react with stirring for 3 hours. A solution of 8.6 g of NaOH in 9 ml of water is added to the reaction mixture and allowed to warm to room temperature.

While stirring, a portion of 25 g of Ν, Ν-dibutylamine is added to the solution and it is heated at reflux temperature for 2 hours. Then, a solution of 8.6 g of NaOH in 9 ml of water is added to the reaction mixture and allowed to react for 3 hours, after which the mixture is cooled to 20 ° C and the organic layer is separated and washed with 140 ml of water. The organic layer is collected, the solvent is evaporated and the resulting solid is added to a three-necked flask equipped with a stirrer, a thermometer and a condenser containing 300 ml of xylene and 14.3 g of bis (hexamethylene) triamine. The reaction mixture is then heated to 142 ° C for 16 hours, cooled to 20 ° C and washed with 400 ml of water. The organic layer is then concentrated in vacuo to give a white solid with a mp. from 68-77'C is obtained.

Elemental analysis ber: C 61.3, H 8.8, N 20.4 exp: C 61.0, H 8.7, N 19.9 1012190! 68

Examples AV-AVIl AIX-AXII AX1V-AXVI. AXVIII-AXX. AXXII and AXXIII

The following compounds are obtained by using the corresponding starting materials analogous to the method described in the above examples: example formula characterization H C O O O ί ^ 3ΓΉ io >> >>

HN N - (CHg) 6 '- N NH

y-fcH sn, p, 20 ° c (Dsc) HSC0 o o O iH CH3 15 CH- Λ HX. I 3 O o O CH_ A6 7 ~ Λ ^ 0-4 V-VCH3 mp. 100 ° C (DSC) H3C_N \ / N ~ \ ^ CH 2 ^ 6 '- N N-CH3. V' Vio ^ 0 20 CH, ° 0 0 1 CH, 3 CH3 3 25 A7 mp. 97 ° C (DSC) Η3 ° Ά °> co-7 V? ° Hs mn— \ h2 v_n nh «. <^ 0 r ° ~ tt 0> -f CH, <^ n3 U CH ^ 3 101 21901 pu 69 H3C 1 ^ 0 ch3 A9 y ~ ^ yVcH3 5 HN \ N ~ (CH2) 6 N NH mp. 99 ° C (DSC)

H3cA ~ ^} ~~ K

CH3 0 cf ΓΑη3 3 ch3 3 10 Λ10 \ j> H3

Hat> CK / - <> - 0 h3 ™ Ρ 75 ° C (DSC> 15 h3cx H ch3 20 H3C ~ Y ^ ^ / - CHg

a "« AA

CH k ^ O mp. 180 "C (DSC)" VL hx-OP *

25 H C 2 V 2 O-C-C 2 2 N / NH

3 O H2 H2> - ^ ch ch3 3 A12 m r QH3

\ I / P O I 3CH

y ~ \ y ~ Y 3 mp. 56 ° C (DSC)

30 HN \ / N ~ \ r ~ N NH

A rtWo 0> iA

OM, U CH3 3 1012190) 70 H * \ JLF *

H3C-V "f-cH3 O ^ N ^ O

V

HC? H: jO O smp. 286 ° C (DSC) Ή * ο »?" · »10 ^ —0 μ--

H3C ^ 1 V Μ H2 H2 'N NH

3 ch3 0 0 ch2 y_y 1 r> ch3 ο υ ch 3 15 'HaC' / xn / \ CH3 h3c h ch3 20 CH3 pij h3c i, S / s H.C-V> - ^ 3 A15 1 Λ smp. 127 ° C (DSC)

CT N O

Λ CH, 25 h C ί ”3 0 I _ƒ VV’ ’“ H rSrCHr0 ^ 2jN-OH3 oH>

Hsc I.h ^ 0 Ο ch3 1012190 71

A16 H C? Η> Ο <λ? W “P 54-58 ° C

5 fii-i h2 h, Hr HC-NW CN N-CH3 h ^ o ^ 0 ^ ^ 0 h '10 ch3 _u H, CI 3 CH3 h3c — y nt-ch3, 5 QS vv5 ^ A18 / N ^ N Ν -Λ M / \ w rH mp. 190 ° C (DSC)

Hf ^ ^ N-CH3 ch3 o ΝΎ "Ν H3cO_ ^ i ° CHa

h3c-n. n I

20 Λ ~~ ^ I

H'c CH3 ° ° γΝγ °

^ TVA

H3 ° iHsCH3 25 A> 9 Η, Ο ^ ΙΙΥ VJ ^ CH3 mp. 78 ° C (DSC)

Ην ·; ν— (CH,) - N NH

H C- ^ 1 \ c> Γ'ΟΗ, 30 1 CHS ° 0 CH, 1012190 72 A20 H3C ^ O 0 ^ 3Ch3 5 H3c-r / \ i— (ch2) —n n-ch3 H3C ^ 7o ch3 υ υ CH3 3 'H NMR (300 MHz, CDCbyppm: 3.72 (t, 4H); 2.32 (s, 6H); 1.48 (m, 4H); 1.36 (s, 10 24H); 1 .24 (m, 12H)

A22 R-NH- (CH2) 6-N (R) - (CH2) 6-NH-R with m.p. 66-72 ° C

H3C? Ha CH3 15 Η30-νΝΝγ-0Η3

R is Cr "N ^ O

C.Hq Y O CH „

An 1-. VV 3 H9C ^ Y Y N-CH3 VN ff — k T cT ^ CH,

Elemental Analysis: Calc: C 62.3, H 9.0, N 19.6; exp: C 61.7, H 8.9, N 19.2 Η, ^ Ο Υ- h = cO> Ych '30' H NMR (300 MHz, CDCl3) / ppm: 3.69 (t, 4H) ; 3.58 (m, 2H); 2.4 (m. 4H); 1.73 (m, 4H); 1.45 (m, 26H); 1.22 (m, 26H).

10121901

Example B1: Stabilizing effect against light in polypropylene slabs.

73 B: Application Examples 5 lg of each of the compounds shown in Table A and 1 g of tris (2,4-di-tert-butylphenyl) phosphite, 0.5 g of pentaerythritoItetrakis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) -propionate], 1 g of calcium stearate and 1 g of Filofin Blue 4G are placed in a turbo mixer with 1000 g of polypropylene powder (MOPLEN ™ SSF) with a melt index of 3.7 g / 10 minutes (measured at 230 ° C and 2 , 16 kg) mixed.

The obtained mixtures are extruded at a temperature of 200-230 ° C

to obtain polymer granules, which are then injection-molded at 200-220 ° C into slices of 2 mm thickness. The resulting slices are exposed in a Model 65 WR Weather-O-Meter (ASTM D2565-85) with a black background temperature of (63 ± 3) ° C until surface brittleness (chalk formation) begins. Further samples are exposed until a roughness parameter Ra = 0.5 µm is reached; the evaluation takes place using a surface texture measurement unit (Surtonic ™ model 3+; Lc = 0.8 mm; Ln = 4.0 mm, Lc is the cut length, ie the length of the reference line used to identify of the irregularities that characterize the surface and Ln 20 is the total evaluation length).

A slab of polypropylene made under the same conditions as above, but without the addition of the compounds of the invention, is exposed for comparison.

Table A shows the required exposure time in hours. The longer the time, the better the stabilizing effect.

Table A

Stabilizer Ra = 0.5 pm after (hours) Time to chalk (hours) without stabilizer 500 connection of example A12 3200 3450 connection of example Al 3 4090 4020 connection of example Al6 3580 3450 1012190

Example B2: Stabilizing effect against light in polypropylene tapes.

74 µg of each of the compounds listed in Table B and 1 g of tris [2,4-di-tert-butylphenylphosphite, 0.5 g of pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) - 5 propionate] and 1 g calcium stearate are mixed in a turbo mixer with 1000 g polypropylene powder (MOPLEN ™ SSF, melt index of 3.7 measured at 230 ° C and 2.16 kg).

The blends are extruded at 200-220 ° C to obtain polymer granules, which are then converted into reinforced tapes 50 µm thick and 2.5 mm wide using a semi-industrial type machine (® Leonard-Suirago (VA) - Italy) and work under the following conditions:

Extruder temperature: 200-230 ° C Head temperature: 240-260 ° C

15 Stretch ratio: 1: 6

The tapes thus prepared are placed on a white card and exposed in a Weather-O-Meter 65 WR (ASTM D2565-85) with a black background temperature of (63 ± 3) ° C.

The residual tame is measured, using a constant speed tensometer, on a sample taken after different exposure times to light; from this, the exposure time (in hours) required to halve the initial toughness (T50) is determined.

By way of comparison, tapes made under the same conditions as above, but without the addition of the stabilizers of the present invention, are exposed. The results are shown in Table B.

Table B

Stabilizer T50 (hours) without stabilizer 500 connection of example A8 1640 connection of example AIO 1610 connection of example A13 2110 connection of example Al6 1910 1012190

Example B3: Stabilizing effect against light in polypropylene fibers.

75 1 g of the compound shown in Table C below, together with 1 g of 5 calcium stearate, 2.5 g of T1O2 (Kronos ™ RN 57) and a mixture of 0.5 g of calcium monoethyl-3,5-di-tert -butyl-4-hydroxybenzylphosphonate and 0.5 g of tris (2,4-di-tert-butyl-phenyl) phosphite are added in a turbo mixer with 1000 g of polypropylene powder (Moplen ™ FLF 20; melt flow index 12.2 g / 10 min., measured at 230 ° C and 2.16 kg).

The mixtures are extruded at 190-230 ° C to yield granules; these are then converted into fibers using a semi-industrial type device (Leonard-Sumirago ™ (VA), Italy) under the following conditions:

Extruder temperature: 200-230 ° C Head temperature: 255 ° C

15 Stretch ratio: 1: 3.5

Count: 11 dtex per filament

The fibers produced in this way are exposed to a white piece of cardboard in a weather-O-Meter ™ Type 65WR with a black background temperature of (63 ± 3) ° C, according to ASTM D2565-85. After different exposure times, the residual tensile strength of the samples is measured using a constant speed tensometer. Then, the exposure time T50 required to halve the initial tensile strength is calculated. The results are shown in Table C below. The amount data is based on the weight of the polypropylene used.

25

Table C: Duration of the exposure (Tso / hour) for halving the tensile strength

Stabilizer T 50 / hour none 300 AXXI 1100 AXXII 1280

The fibers stabilized according to the invention have excellent toughness.

1012190

Example B4: Stabilization of polyethylene films 76

The additives listed in Table D below are added via a master batch in a turbo mixer with LDPE pellets (Riblene ™ FF 29; d = 0.921 g / cm; MFI (190 ° C / 2.16 kg) = 0.60 g / 10min.) mixed. The mixtures are extruded at 200 ° C to give granules which are converted into 150 µm thick films by molding (170 ° C / 3 min.).

Some of the films are treated with pesticides by preserving them prior to WOM-10 exposure at 30 ° C for 20 days over a concentrated solution of VAPAM ™ in water (1: 1 by volume) without direct contact with the solution.

VAPAM ™ (BASLINI SpA, Treviglio / BG, Italy) is an aqueous solution of 382 g of metam sodium of the formula CH3-NH-CS-SNa per liter.

The film samples are then placed in quartz tubes and exposed to a white piece of cardboard in a Weather-O-Meter ™ (WOM) Type 65 WR with a black background temperature of (63 ± 3) ° C. The degradation process is followed by measuring the carbonyl increase in the sample with a Fourier Transform Infrared Spectrophotometer. A large carbonyl increase indicates a large breakdown. Results 20 are shown in the following Table D (arbitrary units). The amount data is based on the weight of the polyethylene used.

Table D: Increase of the carbonyl concentration (iCO) after the displayed exposure 25 (WOM)

Stabilizer iCO after 875 hours WOM iCO after pesticide treatment and 765 hours WOM none 0.4 0.8 0.3% A21 0.037 0.072 0.3% A22 0.046 0.078

It is clear that the stabilizer according to the invention provides an effective stabilization of PE films, both with and without pesticide treatment.

1012190

Example B5: Stabilization of a gray pigmented polycarbonate / ABS mixture.

77

A commercially available PC / ABS mixture (Cycoloy ™ MC 8002; 50/50 w / w mixture of PC and ABS), pigmented with 1 wt% Gray 9779, is stabilized by adding 1 wt. % 2- (2, -hydroxy-3 ', 5, -bis (1,1-dimethyl-benzyl) phenyl) benztriazole (C) and 0.5% by weight of the compound shown in Table E. A sample containing only 1% by weight of the benztriazole stabilizer and an unstabilized sample are for comparison. Izod rods (2.5 "L x 0.5" W x 0.125 "W) are manufactured by injection molding with a BOY 30 machine, temperature of the drum 475-515 ° F, nozzle temperature 515 ° F. Accelerated weathering is performed using an Atlas Ci65A Weather-o-meter (XAW) operating in "dry XAW" setting (ASTM G26-90 method C). after regular intervals, the color change ΔΕ is determined according to DIN 6174. The results are shown in Table E.

15

Table E: Color change (ΔΕ) of gray pigmented PC after the displayed irradiation time

Irradiation time: 94.8 hours 500.5 hours 999.7 hours 1249.0 hours

Stabilizer ΔΕ ΔΕ ΔΕ ΔΕ none ï ^ 5 6 ^ 9 9 ^ 8 ÏËÖ C 0.7 4.2 7.7 9.0 C + All 0.5 3.1 6.2 7.2 C + A14 0.2 2.3 5.4 7.0 C + A4 0.3 2.1 5.0 6.5 C + A17 0.3 1.7 4.3 5.7 20 Example B6: Stabilization of a white pigmented polycarbonate / ABS mixture.

Samples are prepared from a commercially available PC / ABS mixture (Cycoloy ™ MC 8002; 50/50 w / w mixture of PC and ABS as described in Example B5, except that T1O2 (Tiona ™ RCL-4 rutile ; SCM Chemicals) is used as pigment (101 2190 78). Weathering and determination take place as described in Example B5; the results are shown in Table F.

Table F: Color change (ΔΕ) of white pigmented PC after the displayed irradiation time

Irradiation time: 499.3 hours 999.8 hours 1249.3 hours

Stabilizer ΔΕ ΔΕ ΔΕ none TÜ6 21 ^ 8 23/7 C 6.0 15.7 17.4 C + All 2.6 10.2 11.7 C + A14 23 9.3 11.3 C + A4 2.7 9.6 11.4 C + A17 2.2 9.2 10.7 PC / ABS samples stabilized according to the invention exhibit excellent color stability.

10

Example B7: Gloss and impact resistance of stabilized PC / ABS

The gloss and impact strength of further examples prepared and subjected to weathering as shown in Examples B5 and B6 are determined.

15 Gloss: 2 "x 2" injection molded slices are removed and replaced every interval. The measuring device is a BYK-Gardner Haze-Gloss Laboratory Reference Instrument.

Splice Resistance Test: 10 same rods are used for each test interval, subjecting the exposed surface to the impact test. The test is performed according to ASTM D4508-90 using a TMI Monitor / Impact Tester.

PC / ABS samples stabilized according to the invention with 0.5% by weight of the compound of Example A4 or A17 exhibit excellent gloss retention and excellent impact strength.

25 1012190 79

Example B8: Stabilization of a 2-layer metallic finish

The light stabilizers to be tested are dissolved in 30 g of Solvesso® 100 and tested in a clear coat with the following composition (parts by weight): 5

Synthacryl® SC 303 27.51

Synthacryl® SC 370 2) 23.34

Maprenal® 6503) 27.29

Butyl acetate / Butanol (37/8) 4.33

Isobutanol 4.87

Solvesso® 150 4) 2.72

Crystal Oil K-305) 8.74

Leveling aid Baysilon® MA 6) 1.20 100.00 1 Acrylic resin, ®Hoechst AG; 65% solution in xylene / butanol (26: 9) 2 Acrylic resin, Hochst AG; 75% solution in Solvesso® 1004 3 Melamine resin, ®Hoechst AG; 55% solution in isobutanol 10 4 Mixture of aromatic hydrocarbons, boiling range: 182-203 ° C (Solvesso® 150) or 161-178 ° C (Solvesso® 100); producer: ®Esso 5 Mixture of aliphatic hydrocarbons, boiling range: 145-200 ° C; producer: ®Shell

6 1% in Solvesso® 150; producer: ®Bayer AG

1% of the light stabilizers to be tested are added to the clearcoat based on the solids content of the varnish. As a comparison, a clear coat is used that does not contain light stabilizers.

The clearcoat is diluted with Solvesso® 100 to spray viscosity and is sprayed onto a prepared aluminum panel (Uniprime Epoxy, silver metallic basecoat), which is baked at 130 ° C for 30 minutes, with a dry film thickness from 40-50 µm of the clear coat is obtained.

The samples are then subjected to weathering in an Atlas ® UVCON weathering unit (UVB-313 lamps), in a cycle comprising 4 hours of UV irradiation at 70 ° C and 4 hours of condensation at 50 ° C. Then the surface gloss 1012190 80 (20 ° gloss as defined in DIN 67530) of the samples is measured at regular intervals. The results are shown in Table H.

Table H:

Light stabilizer 20 ° * gloss as defined in DIN 67530 after ... hours of weathering in the ®UVCON (UVB-313) 0 hours 400 hours none 93 77 A7 93 ”83 _ _ - A9 93 86 _ _ _ __ - _ AÏ3 93 89 5 * high values indicate good stabilization

The results listed in Table H show that the samples stabilized with a stabilizer according to the invention have a better weathering stability (retains gloss) than the unstabilized sample.

10

Example B9: Stabilization of thermoplastic olefins

Molded test samples are manufactured by injection molding of thermoplastic olefin pellets (TPO pellets) containing pigments, a phosphite, a phenolic antioxidant or hydroxylamine (HA), a metal stearate, ultraviolet light absorbers (UVA) or sterically hindered amine stabilizers (HALS) or a mixture of UV absorbers and sterically hindered amine stabilizers as described below.

Pigmented TPO pellets are prepared from a pure pigment or pigment concentrates, stabilizers, co-additives and a commercially available thermoplastic olefin by mixing the components in a Superior 1/1 "single worm extruder with a general purpose universal screw (24: 1 L / D) at 400 ° F (200 ° C), cooled in a water bath and pelletized The resulting pellets 1012190 81 are using a BOY 30M souss machine at approximately 375 ° F (190 ° C) formed into 2 "x 2" slices of 60 mil (0.006 inch thick).

Pigmented TPO formulations consisting of polypropylene mixed with a rubber modifier, the rubber modifier being a copolymer that has reacted in situ or is a mixed product that is copolymers of propylene and ethylene with or without a temary component such as ethylidene phenomenon, are stabilized with a base stabilization system consisting of an N, N-dialkylhydroxylamine or a sterically hindered phenolic antioxidant with or without an organophosphorus compound.

All additive and pigment concentrations in the final formulations are expressed as weight percent based on the resin.

The formulations contain thermoplastic olefin pellets and one or more of the following components; 0.0% - 2.0% pigment, 15 0.0% -50.0% talc, 0.0% - 0.1% phosphite, 0.0% - 1.25% phenolic antioxidant, 0.0% - 0.1% hydroxylamine, 0.05% - 0.10% calcium stearate, 0.0% - 1.25% UV absorber, 0.0% - 1.25% sterically hindered amine stabilizer (HALS).

The components are dry blended in a tumbler dryer before extrusion and molding.

Test plaques are applied in metal frames and exposed in an Atlas Ci65 25 Xenon Are Weather-o-meter at a black background temperature of 70 ° C,

a

0.55 W / m at 340 nanometers and 50% relative humidity with alternating light / dark cycles and spraying with water (Society of Automotive Engineers - SAE J 1960 test procedure). Samples are tested at approximately 625 kilojoule intervals by taking color measurements using an Applied Color Systems spectro-30 photometer in the reflectance mode according to ASIM D 2244-79. The data collected included delta E, L *, a * and b * values. Gloss measurements are performed using a BYK-GARDNER Haze / Gloss Meter at 60 ° according to ASTM D523.

101 2190 '82 UV exposure test

Test specimens are made from a commercially available polyolefin blend (Polytrope TPP 518-01; supplier A. Schulman, Inc .; Akron, Ohio, USA), using 60 mil thick 2 "x 2" injection molded slices are exposed to UV radiation under SAE J 1960 - Exterior Automotive conditions.

The control sample contains as stabilizer formulation compound A as shown in the following table, 0.2% by weight of compound B and 0.1% of a 1: 1 mixture of tris (2,4-di-tert-butylphenyl) phosphite and 1 part of pentaerythritol tetrakid [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] in the final resin formulation commonly used in industry to influence UV stability.

Samples 1-3 stabilized according to the invention contained 0.05% dialkyt-hydroxylamine in the final resin formulation as base stabilization and 0.2% by weight of compound C cost stabilizer.

Compound A is bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate; compound B is poly [[6 - [(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] - [[(2,2,6,6-tetramethyl) 4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]]; CAS No. 70624-18-9; compound C has the formula R-NH- (CH2) 3-N (R) - (CH2) 3-NH-R, with R being 20 9h3 9H3

Xf-XlC (HrN> N ^ NsC, H9

NVN

25 (CAS) No. 106990-43-6). Compounds A, B and C are commercially available stabilizers (Ciba Specialty Chemicals Ine.).

All samples contained 15% talc, 0.2% 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzo triazole, 0.1% calcium stearate and 0.25% Red as a color make-up 3B and pigment Red 177, Cl # 65300.

All additive and pigment concentrations in the final formulations are expressed as weight percent based on the resin.

1012190 83

Table I: UV exposure test of Polytrope TPP slabs

Sample NECK delta E Gloss% retains gloss 3000 kJ / m * 3000 kj / m ^ 3000 kj / m2

Control 0.20% A 4/7 M M% 1 0.20% A9 L9 2L8 32.1% 2 0.20% A19 ^ 2 27 ^ 2 40.6% 3 0.20% A13 2β Ϊ5 /? 27.3%

The samples exhibit exceptional light degradation resistance when stabilized with light stabilizer systems comprising a piperazinedione according to the present invention.

In all cases, the light stabilized formulations exhibit much greater resistance to photo degradation than unstabilized samples, which fail rapidly under the UV exposure conditions shown above.

1012190

Claims (15)

1. R15 <co-R8) - Ris <c ° -Ra) r15 when s is 8, A C8 -C10 alkane octayl; C8 -C12 alkane octayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups with the formulas (Villa) - (Vlllb) - (Re-CO) -R, s R, 5 <C ° -Rb> - 20 \ / - (RfCO): R ,, - NN ^ X- R ', 5 -Χγ N - R1S1C0-R8) - N ^ NN ^ N - (Rg-CO). RIS N N-R15- (CO-R9) - (Vma) - (Rc / CO). R15 25 - (R, -CO): R15 R, 5 <CORe) - - (Ra-CO) - R15- NN ^ X-R '^ - N R'ü N ^ N' Rn fCO-Rg) - T ^ n ^ n n4m (Vlllb) I in LK T - (R8-CO): R) 5 XZ ^ NN -R ^ CO-R,) .— X- R1S- (CO-Re) ~ R15 <CO-R8) - 1012190 the index i is zero or 1; Re and R9 and R28, R29, R30, R31, R32 and R33 are independently methylene, and when R5 is not hydrogen, additionally include ethylene; R 1 C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl, C 7 -C 15 phenylalkyl which is unsubstituted or is substituted on the phenyl ring with a moiety selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; R12, R13 and R14 independently of each other C2-C10alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-; C4 -C12 alkenylene; A composition comprising (A) a synthetic organic polymer selected from the group consisting of polyoxy-5-methylene, a mixture of a polycarbonate with an acrylonitrii-butadiene-styrene terpolymer and a coating system based on a functional acrylate resin and a cross-linking agent and (B) as a stabilizer a compound of the formula I or II 10 r 1 R.-N N - A (0 L Ri ° JS 15 z, - if R'-X - z * N ^ N 20} (11) R 5 -Nn, N- <R 19) -R 15 R 3-> H 0 L r; 0 J 25 where p is in the range 1 to 10; s is in the range from 1 to 8; if s is 1, 30. C 1 -C 18 alkyl; C2 -C18 alkyl which is substituted with NH2, hydroxy, halogen and / or OR10 or is interrupted by -O-, -NH- and / or -NR10-; or A is C 1 -C 18 alkyl substituted with -COOR 11 offenyl; when s is 2, 1012190 A C2 -C10 alkylene; C4 -C12 alkenylene; C3-C15 alkylene substituted with one or more OH and / or interrupted by one or more oxygen, phenylene, C1-C4 alkyl-phenylene, -COO-, -CONH-, 5 —ΧγΝγΧ_ "X 'IN ^ n, -NH- and / or -NR.0-; Am 'AmA-zz NZ is s 3, The composition of claim 1, wherein the mixture of a polycarbonate with an acrylonitrile-butadiene-styrene terpolymer of component (A) is a mixture of 10 to 90 parts by weight of polycarbonate with 90 to 10 parts by weight of acrylonitrile-butadiene-styrene terpolymer. 1012190 Composition according to claim 1, which contains as further component (C) a UV absorber from the class of the benzotriazoles, o-hydroxyphenyl-s-triazines and / or benzophenones. 4 A, - Λ Re Γ \ χ4 χ5γρ30 \ (Va) 15 r / ° ° R29 when s is 6, A C6 -C10 alkane hexayl; or one of the groups of formulas (Vlb) - (Vlf) is 20 - (R9-CO) - r, 5 R15 <co-r29) - - '(Rb-CO) r R15- N ^ N- R15- (CO-R28) .- ΝγΝ (R ^ -COj-R ^ -NR ^ -tCO-R ^) .- (Vlb) 25 - (r8-co) -r15 R, 5 <c ° -r8) - - (R „-CO): R, 5- NN ^ x- R'15 -Χγ N · R15 iCO-R„) - N ^ N (Vlc) 30 - (Re-CO) —R1S — X XR (5 - (CO-R9) .— 1012190 R, 5 (CO-R8) - 5 <Rh-CO): R ,, - x γΝ γΧ- R-15 -XN γ N - R15iCO-Re) - ΝγΝ N ^ N - (R (J-CO) - R ,, - X N-R15 - (C0-R9) - (Fld) Ri5- (co-Ra) - 10 -flVCO): R1s R15 <CO-R8) - - (R .-CO): R15 - N γΝ γΧ-R'i ^ —N ^ -R «-Χγ N γ ** 'R, ^ CO-Re) - ΝγΝ Ϊ j? N ^ N (Vie) ZZ ^ N ^ N-Rl5 - (CO-R.) - Z, 5 R, 5 <C ° -Ra> - - (R.-C0): R1S- X γΝ γΧ-R ' —N-R'l-Χγ NYX - RIS - (CO-R,), - n ^ N n ^ nn ^ nt XXI (V, f) 20 - (ReCO) .R15— XY ^ N ^ XR ^ -iCO -RJ-XR 4 -C 0 -R 5 - R 5 <c ° -Re) - when s is 7, AC 7 -C 10 is alkane heptayl; if s is 8, 25. C8 -C10 alkane octayl; whether one of the groups of the formulas is (Villa) - (VUIb); the index i is zero or 1; R1 and Ry and Rig, R29, R30, R31, R32 and R33 are independently methylene; R10 is C1 -Ck alkyl, C1 -Cx alkanoyi, C5 -C12 cycloalkyi, C7 -C15 phenylalkyl; R 12j Rn and R 14 independently of each other are C 2 -C 10 alkylene, C 3 -C 12 alkylene substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; C4 -C12 alkenylene; 1012190) Ris and R '15 independently of each other C 2 -C 10 alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-; R 16 is C 3 -C 10 alkane triyl; The composition of claim 1, wherein in the compound of formula 1 (component B) s is in the range of 2 to 6; when s is 2, A is C 2 -C 10 alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; or a group of the formula -R.8-COO-R12-OCO-R9- (11a); if s is 3, A is a group of formula (lila) 15 4. ^ 0 <"'*> 0. o. Λ Λ / Rf XrR ,, R'— x, K 20 if s is 4, A is of the groups with formulas (IVa) or (IVd) is 25 0 1 1? Λ Ral 30 1012190 (R9-CO) - R, 5 R, 5 <CO-R28) - - (Re-CO) - R1S - NN - R1S - (CO-R2B) - 5. ΝγΝ 2 (IVd) if s is 5, A is a group of the formula R17 is C4-C10 alkantetryl; X is -O-, -NH- or -N (Rio) -; Xu X2, X3, X4 are independently -O- or -NH-; and Z means NHR10 or N (Rio) 2. R17 is C4-C10 alkantetryl; Ris is C5-C10 alkane pentayl; X is -O-, -NH- or -N (Rio) -; Xi, X2, X3, Xt, X5 are independently -O- or -NH-; and Z represents halogen, NH2, NHR10, N (R10) 2 or C1 -C4 alkoxy. 10 5 T 2 (IVd) when s is 5, A C 5 -C 10 alkane pentayl; or a group of the formula (Va) is rL 5 N \ ^ N Z2 is H or a radical of the formula ^ 2v / PI; r - H R 5 -N N- (R 9 -C) -R 1 S RrM ° r; o 10 5 NVN NYN (Vile) - (R.-CO): R1S -IXAX - R ^ CO-RJ- ΝςΠιΤ <00-Β8) - R15 (CO-r8) - R ^ ° ^ 10 - (R.-CO, : Rlb - XNX — IR '^ XY VX R- (C °' Re) ^ N-VN 11 X (Vlld) - (Ra-CO), r15 -4 X ^ NAN - B15 - <co-Re) - x - R, 7 ^ -rb) - 5. YV "ϊ Ν'γΝ (Vie) ZZ ^ N ^ NR. ^ CO-R,). - 2 R, 5 <CO-Re) - 10 - (R" -CO): R, rX ^ X- R '- ^ - R', 1-X -γ N γ X '- <CO-Re) - NN Ν' "NN ^ NI XX X (vif) - (Re-CO). R15 x N X "R, s" (CO-Re). X-R 2 CO-R 1 - R 15 (C 10 RB) 15 when s is 7, A C 7 -C 10 alkane heptayl; C7 -C12 alkane heptayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups with the formulas (Vila) - (Vlld) 20 - (Re-CO): R1S R1S <C ° -R8) i - (Rb'CO) r R, s - N γΧ- R'15 · Χγ N - R1S 1CO-Re) - ΝγΝ N ^ N - (Ry-CO) - Rti — XN— R, 5 (CO-R9). (Vila) Rl5- (co-R9) - 25 R1s (CO-Re) - - <Rb-CO): R15 / 5 \, γ R, ___ N - R'ic-X ^ N ^ / N'R> a '(C0'Re) i— - (Re-CO): R15-N N ^ X-R15 f 15 if Ί T Ϊ N ^ N NYN (Vllb) 30. z ^ N ^^ - R16- (CO- R9) r * -R16- (CO-R9) - R15 <co-Re) r τστ2ΐ9ο - (R8-C0): R) 5-X -R '«^ R'5 ΧΥΝΥΧ 5 Rl o (, lla> OIO. 1 ^ Λ ^ R8 ^ Xi-Ri5 R'— x2 R9 10 - (R8-C °) [Ris - X γ'Χ- R, 6 - <C0-R2.) F N ^ / N (tllb) - (R9-CO) j R15 X - (R9-CO). R1S 15 \ - (R.-CO) - R, s - N N ^ X- R, sfCO-Ri8) - z (Hlc) 20 rL \ ^ o J C "d) 0 1 11 '' R 1, 'X' R, 6'xr'R, "" when s is 4, A is C 4 -C 10 alkantetryl; C 4 -C 12 alkanetetryl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups of formulas 30 (IVa) - (IVd) 1012190! 4βγ ° ° Xj ο 5 'β ^' 'χ- "ΒΓχ, 8. i 9 (IVa), Λ R29 1 ° - (Rg-CO) r R, s - X γΝ γΧ- R'15 -Χγ N γ X R1S ^ 0-Πβ) - ΝγΝ (IVb) - (r9-co) - r15 — x xR.5 - (co-r9) - 15 - (R.-CO) .— r15 \ - (Rg-CO) - R15- N γΝ γΧ- R15iCO-R28) -ΝγΝ 20 X-R15- (CO-R2e) - (IVC> - (r9-co) - r, s r1s <co-r28) - - (Rg-CO) r R, s- N γΝ γΝ ~ R15- <CO -R2B) - 25 ΝγΝ [(IVd) if s is 5, 30. C5 -C10 alkane pentayl, f5 -C1 alkane pentayl dst is substituted with OH and / or is interrupted by oxygen, is -NH- or -NR10-; or is one of the groups with the formulas (Va) - (Vc) 10121901 4γΟ Q ο χ / xrV 8 1 χ4> WR30- (Va) i4 II Λ ° M29 io R, 5 <co-Re) - - (R0 -CO) - R15 - X γΝ γχ- R'15 -X γ N - R, s - (CO-R,). - ΝγΝ ΝγΝ (Vb) - (Re-CO). —R1S — XX — R, s - (CO-R9) - 15 - (R9-CO) - R Ri5 (CO-Re) j— - (Re-CO): R15 - N ^ N ~ Rts- (CO-R2e) - N 20 V X-R15- <CO-R2e) - (Vc) when s is 6, 25. Ce-C10 alkane hexayl; C6 -C12 alkane hexayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups with the formulas (Via) - (Vlf) T01219O. X * Γ Λ / 5 "· * _Λ.γχβ χηΛ ^ (Va) ° rA> ° ** 29 ψ 10 - (R9-CO) - R, s ri5 <co-r29) - - (Re-CO) r R) S- NN ^ N- R, s iCO-R28) - 15 (^ m'CO) Γ R15 N ~ R, s ^ CO-R31) - (Vlb) - (RB-CO): Rls R16 <CO -R8) - l / - (Re-CO): R1S - N ^ / X- R'15 -XN N- R, s - (CO-R,) - 20 ΝγΝ ΝγΝ (Vlc) - (R9-CO) R1S X X-Rls - (CO-Rg) - R15 <CO-Re) ~ - (ee-CO) - R15 - X ^ N ^ X-R'1S-XN - R.siCO-R,). - 25 N ^ N - (R9-CO). r, 5 x N — R1S - (CO-r9) .— (Fld) R15- (CO-R9) ~ 30 1012190 - (Re-co) .F ^ ri5 <co-r8) - "(Ra'C ° ) [R, b - N γΝ γΧ - Rii-Χγ N γ Ν / · R '= - <C0-Re) i— 5. A compound of the formula (Γ) or (II) R, .O 5. T (R9-CO). R, 5 X N R, 5 (CO-Rg). (Fld) R5 (CO'Rg). · »10 - (R8-CO): R15 * ^ 15 <C ° -Re) j - (R.-CO) r R, 5- NN X-R'TÜ ij R'ii ΧγN 'R> ^ C ° -Rx) i__ L 5, n ^ n (Vie) TL 1L T i Z ^ N N-R1S - (CO-R,) - Z 15 R15 (CO-Re) - - (Rg-CO) - R15- XN x-R '—- N-R'ii-Xy, NX · R ^ co-Rg) .— N. NN "NN. NIL ϊ T (V! F) - (Rg-CO) · R, 5-XXN XR15- (CO-Rg) - XR- (CO-Re) - 20, R, 5 <C ° -Re> - de index i is zero or 1; R 1, R 2, R 1 and R 4 are independently methyl; R 5 is hydrogen; C 1 -C 18 alkyl; oxyl; OH; C 1 -C 18 alkoxy; C 5 -C 12 cycloalkoxy; C 3 -C 5 al-kenyl ; or R5 is C 1 -C 6 alkanoyl; C 3 -C 5 alkenoyl; C 1 -Ctx alkanoyloxy; glycidyl; or a group is -CH 2 CH (OH) -G, where G is hydrogen, methyl or phenyl; R 5 and R 9 and R 2, R 29, R 30 , R31, R32 and R33 are independently methylene; R10 is C 1 -C 8 alkyl, C 1 -C 6 alkanoyl, C 5 -C 12 cycloalkyl; R 12 is C 2 -C 10 alkylene; or C 3 -C 12 alkylene interrupted by oxygen, -NH- or 30 is -NR10-; R15 and R'i5 are independently C2-C10 alkylene; R17 is C4-C10 alkane metyl; Rik is C5-C10 alkane pentayl; 1012190 X -O-, -NH- or -N (Rio) - Xi, X2, X3, X4, Xs, Xó, X7 and Xg are independently -O- or -NH-; and Z is NHR10, N (R, o) 2 or C1-C4 means alkoxy. 5 R19 C6 -C10 alkane hexayl; C6 -C12 alkane hexayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; X is -O-, -NH- or -N (Rio) ~; Xt, X2, X3, X4, X5, X0, X7 and X8 are independently -O- or -NH-; 10 0 9 H 2 -O- or a radical of the formula N-R; t- (CO-R q) - N N-R; / 15 '91/0/0 r2 15 Z represents halogen, NH2, NHR10, N (Rio) or C1 -C4 alkoxy; Zi has one of the meanings of Z or -X-R'u-XH is and 20. Vz N ^ N R 0 I Z2 H or a radical of the formula 2 \ // Λ; RrT ~ A / Rs-N N- (R 9-C) -R 15 Hr7 ~ \ 0 25 r / 0 5 T Λ λ T - (Re-CO): R5-X Z N N-R ^ CO-R, - X-R15- (CO-RJj-R, 5 <co-Re) - the index is nut or 1; R 1, R 2, R 3 and R 4 are independently C 1 -C 4 alkyl or R 1 and R 2 or R 3 and R 4 together with the carbon atom to which they are attached form a cyclopentyl or cyclohexyl ring; Rs hydrogen; C 1 -C 18 alkyl; pxyl; OH; CH2CN; C 1 -C 6 alkoxy; C5-C12 cycloalkoxy; C3-C8alkenyl; C 1 -C 6 alkynyl; C7-C12 phenylalkyl; C7-C15 phenylalkyl substituted on the phenyl ring with 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; C7-C15 phenylalkoxy; C7-C15 is phenylalkoxy which is substituted on the phenyl ring with 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R5 C 1 -C 6 alkanoyl; C3-C5alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group is -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl; Rg and R9 and R28, R29, R30, R31, R32 and R33 are independently C1 -C4 alkylene; R10 is C 1 -C 6 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl, C 7 -C 15 phenylalkyl which is unsubstituted or substituted on the phenyl ring with a moiety selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R10 is C 1 -C 6 alkyl or C 1 -C 8 alkanoyl substituted with OH, C 1 -C 12 alkoxy and / or a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone group are unsubstituted or substituted with 25 OH, halogen, C1 -C4 alkyl and / or C1 -C18 alkoxy; R 1 C 1 -C 18 alkyl; C 2 -C 18 alkyl substituted with NH 2, NHR 10, N (Rio) 2, nitro, hydroxy and / or C 1 -C 6 alkoxy; C3 -C18 alkenyl; C5-C12 cycloalkyl; C5 -C12 cycloalkyl which is substituted with C1 -C4 alkyl and / or is interrupted by -O-; Ris and R'is independently C2-C10 alkylene; C3-C12alkylene substituted by OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-; Rif, C3-C10 alkantriyl; C3 -C12 alkane triyl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; 10121905 Rn C4-C10 alkantetryl; C 4 -C 12 alkanetetryl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; Ris C5-C10 alkane pentayl; C5 -C12 alkane pentayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; 5. XN ^ H VN (V ,, C) N ^ / NI II IT v ^ n ^ XR ^ CO-RJ - N \ Ri5 <CO'R ·) ·· - (R -CO) R, —X \ 1 \ B 1 16 \ R „(CO-r8) - R, 5 <co-R *> r 10 - (Rg-CO) r R15 - XN ^ / X-fV-s Ijl R'ii Χ-γx R <s- <C0-R8> i— I 'nn ^ n N .n VI ï T (Vlld) - (Ra-CO). R (5-XXN N-Rl51CO-R8) i XR ^ CO-Rglj | R 5 ^ CO-R 8 - 1,5 R 5 <CO-R 8) r when s is 8, A C 5 -C 10 alkane octayl; CV-C12 alkane octayl substituted with OH and / or interrupted by oxygen, -NH- or -NRt0-; or one of the groups with the formulas (Villa) - (Vlllb) is 20 - (Re-CO) -Rl5 R) 5 <CO-Ra) - - (RB-CO) - R1S - N ^ X- R'1S - XN - Rts - <CO-RB) - N ^ NN ^ N 25 - (Ry-CO). R —NN — R - (CO-R) - 9 '16 I \ H'5 (Villa) "(R9-CO) .— R15 Ris- (CO'Re> ~ 1012190 -.« Ι - (Re-CO ): R, s Rt5 <CO-Re) - \ / - (Re-CO) 7 R1S - NN XR> - N-R'ig-Xy, NNR1S - (COR,) - L 5. n ^ nn 'N (Vlllb) A compound of the formula (Γ) or (II) according to claim 5, wherein p is in the range of 2-6, s is in the range of 2 to 8; R 1, R 2, R 3, and R 4 are independently methyl or ethyl; R5 hydrogen; C1-C18 alkyl; oxyl; OH; CH2CN; C 1 -C 18 alkoxy; Cs-Cn cycloalkoxy; C3 -C8 alkenyl; C7-C12 phenylalkyl; C7-C15 is phenylalkoxy; or R5 C 1 -C 6 alkanoyl; C3-C5alkenoyl; C 1 -C 6 alkanoyloxy; glycidyl; or a group is -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl; if s is 2, 20. C3-C12alkylene substituted by OH and / or interrupted by oxygen, -NH- or -NR to-, C4-C12 alkenylene, or one of the groups of formulas (11a) - (lie) -R8-COO-R12-OCO-R9-; -R8-CONH-R13-NHCO-R9-; -Re-COO-R, 4-NHCO-R9-; (Ha) (Nb) (He) 25 - (Rs-coirR ^ XyN ^ z (member) - (R9-C0) - r, 6-x 30 1012190) - (η, -co), - R «\ - (R ^ COl-R ^ -N ^ N ^ Z 5 n 'n (lie) z and when R5 is not hydrogen, A also includes C2-C10 alkylene; C2-C10 alkylene interrupted by phenylene or C1-C4 alkylphenylene ; 10 if s is 3, A is C3-C10 alkane triyl; or one of the groups of the formulas (Ilia) - (Hid) is rI .o (»« a) 15. I 0 ^ A Λ / R8 XrR, 5 R'ïT-X2 R9 - (R8-CO) r R, s - x ^ X- R1S iCO-R28) - 20 ΝγΝ (lllb) - (R9-co) - r15 - X - (Rg-CO). Ri5 25 - (R8-CO) r R1S- NN ^ X- R. ^ CO-R *) - ΝγΝ z (die) 1012190: rL ^ ° (Hid) 5.o O- IO - A Rf X, X2 R9 when s is 4, A is C 4 -C 10 alkantetryl; or one of the groups of formulas (IVa) - (IVd) is 10 X 3.5 ArRkV X, (IVa) BA ^ 29 20. CVCO) r R15- X ^ X- -XX - R, 5 - <CO-R8) - N ^ NN / N y γ (ivb) - (R9-CO) - r15— X X-R1S - (C0 -R9) -, c - (R9-CO) R1S \ - (R.-CO): R, 5 - N ^ X ~ Rl5- (CO-R2e) - NyH X-R1S- (C0-R28) - ( , Vc) 30 1012190 - (Rg-CO) - R, s R15 <C0-R28) - - (R8-co) - ris - nn ^ N- R151CO-Rm) - NVN A compound of the formula (Γ) according to claim 5, wherein s is in the range from 2 to 6; R1, R2, R3 and R4 are independently methyl or ethyl; Rs hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH2CN; C 1 -C 18 alkoxy; C5 -C12 cycloalkoxy; C3-15 Cs alkenyl; C7-C12 phenylalkyl; C7-C15 is phenylalkoxy; or R5 C 1 -C 8 alkanoyl; C3-C5alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group is -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl; when s is 2, A is C3-C12alkylene substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; C4-C12alkenylene; or a group of the formula (Ha) is -R8-COO-R12-OCO-R9-; (Ha) and when R5 is not hydrogen, A also includes C2-C10 alkylene; when s is 3, A is C 3 -C 10 alkanetriyl; or one of the groups of formulas is (lilac), (IHb) or (Illd); When s is 4, A is C4-C10 alkantetryl; or is one of the groups of formulas (IVa), (IVb) or (IVd); when s is 5, A is C5-C10 alkane pentayl; when s is 6, 30. is one of the groups of formulas (VIb) - (Vlf); the index i is zero or 1; Rg and R9 and R28, R29, R30, R3i, R32 and R33 are independently methylene; R 10 is C 1 -C 8 alkyl, C 1 -C 8 alkanoyl, C 5 -C 12 cycloalkyl; 1012190 Ill R-12 C2-C10 alkylene; C3 -C12 alkylene which is substituted with OH and / or interrupted m by oxygen is -NH- or -NR10-; R15 and R'is independently of each other are C2-C10alkylene; R 16 is C 3 -C 10 alkane triyl; A compound of the formula (Γ) according to claim 5, wherein s is 2, 3, 4 or 6; R1, R2, R3 and R4 are methyl; R5 hydrogen; C 1 -C 8 alkyl; C 1 -C 18 alkoxy; cyclohexyloxy; allyl; benzyl; acetyl; C3 -C4 alkenoyl; glycidyl; if s is 2, 15. C3 -C10 alkylene substituted with OH or interrupted by oxygen, -NH- or -NR.10-; or a group of the formula -R8-COO-R12-OCO-R9- (Ha); and when R 5 is not hydrogen, A also includes C 2 -C 10 alkylene; when s is 3, A is a group of the formula (lila); when s is 4, A is a group of the formula (IVa) or (IVd); When s is 6, A is a group of the formula (Vie); the index i is zero; R1 and R9 and R2g, R29, R30, R31, R32 and R33 are methylene; R10 is C1 -C8 alkyl, formyl, acetyl or cyclohexyl; R 1 C 2 -C 10 alkylene; or C3-C10alkylene interrupted by oxygen; Ru and R15 are independently C2-C10alkylene; Rn is C4-C10 alkantetryl; X is -NH-; Xi, X2, X3, X4 are -O-; and Z means N (RIO) 2. 8. X Χ5γΗ30 \ (Va) I4 Ϊ IS rA 0 ^ 29 when s is 6, A is one of the groups with formulas (VIb) - (Vlf) 20 - (Re-CO) —R «ri5 <co- r29) - - (Ra-CO) r R15 - N ^ N- R15fCO-R2e) - ΝγΝ 25 (R30-CO) - R15 -N- R15iCO-R31) .- (V, b) - (R8-CO) : Ri5 R15 <CO-Rb) - \ / - (Ra-CO): R) 5- N ^ X- R'1S -XN - R ^ CO-R,) - N ^ NN ^ N (Vie) 30. T - (R9-CO) j R) 5 X X-R15- (CO-R9) .- 1012190) R15 <co-R8) f- - (Re-CO) - R15 - X ^ X ~ R ' i5 -x N R15 iCO-R8) - N ^ NN ^ N 9. A composition comprising A) an organic material sensitive to damage by light, oxygen and / or heat and B12 as a stabilizer a compound of the formula Γ or II according to claim 5. 10. A composition according to claim 9, which as organic material comprises a thermoplastic organic polymer or a binder for a coating or a photographic material. R15 and R15 | independently of each other C2 -C10 alkylene; C3-C12alkylene substituted with OH and / or interrupted by oxygen, phenylene, C1 -C4 alkylphenylene, -NH- or -NR10-; R10 C3-C10 alkane triyl; C3 -C12 alkane triyl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; Rn C4-C10 alkantetryl; C 4 -C 12 alkanetetryl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; Ris C5-C10 alkane pentayl; C5 -C12 alkane pentayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; R19 C6-C10 alkane hexayl; C6 -C12 alkane hexayl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; X-O -, - NH-or -N (R, O) -is; Xi, X2, X3, X4, X5, X0 are independently -O- or -NH-; 25. V4, r3 Y -O- or a radical of the formula ^ -R _ (C0.R j — n '\ | —r, * /'> ~ (R1 o r2 30. halogen, NH2, NHR10, N (Ri0) 2 or C1-C4 means alkoxy; Zi has one of the meanings of Z or -X-R'u-XH and is 101 2190 w 10 R5-N N - A O w o _ 4 —J s 15 Γ z ’- 1f χ — R'— x - z * N ^ .N« p T r5-N N- (R f9) -R 15 At ° R / 0 J p where p is in the range of 1-10; s is in the range from 1 to 8; R 1, R 2, R 3, and R 4 are independently C 1 -C 4 alkyl; R5 hydrogen; C 1 -C 18 alkyl; oxyl; OH; CH2CN; C 1 -C 6 alkoxy; C5-C12 cycloalkoxy; C3-C8alkenyl; C3 -C8 alkynyl; C7 -C1 phenylalkyl; C7-C15 phenylalkyl substituted on the phenyl ring with 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; C7 -C18 phenylalkoxy; C7-C15 is phenylalkoxy which is substituted on the phenyl ring with 1, 2 or 3 radicals selected from C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or R5 C 1 -Q alkanoyl; C3-C5alkenoyl; C 1 -C 18 alkanoyloxy; glycidyl; or a group is -CH2CH (OH) -G, wherein G is hydrogen, methyl or phenyl; 10121901 when s is 1, A is C 2 -C 18 alkylene substituted with OR30, where R30 is C 1 -C 8 alkyl -. Or is C 1 -C 6 alkanoyl which is substituted with a benzophenonyl or benzophenonyloxy radical, wherein one or both phenyl rings of the benzophenone group are unsubstituted or substituted with OH, halogen, C 1 -C 4 alkyl and / or C 1 -C 6 alkoxy; 5 when s is 2, A is C3-C15alkylene substituted with one or more OH and / or interrupted by one or more oxygen, -NH- and / or -NR10-; -Vrx- YC ~ M V 'ΛΑ, or A is C3-C15 alkylene substituted with OH and is interrupted by phenylene, C1-C4 alkylphenylene, -COO-, -CONH-; or A is C4-C12 alkenylene or one of the groups 15 of formulas (Ila) - (He) -R8-COO-R12-OCO-R9-; -Ra-CONH-R, 3-NHCO-R9-; -R8-COO-RJ4-NHCO-R9-; (Ila) (llb) (llc) 20 - (Rb-CO): R, 5-XyYz ΝγΝ (member) - (RB-CO) j — R, s "X 25 - (R» -co) r "Ris - (Re-coirR ^ -N ^ N ^ z JL ·? · Cle) Z and when R5 is not hydrogen, A also C2-C10 alkylene; C2-C10 alkylene interrupted by phenylene or C1-C4 alkylphenylene; when s is 3, 1012190 A C3-C10 alkane triyl; C3 -C12 alkantriyl which is substituted with OH and / or interrupted by oxygen is -NH- or -NR10-; or is one of the groups with the formulas (Ilia) - (IHd) 10 O vi 1 / O yXi ^ V'r ^ V'X '^' R18 \ 10 R29 - (R9-CO). R, j ri5 <co-r29) - - (R8-CO): R15 - N N - R, 5 - <CO-R28) .- N. N 15 I (R30-CO) .- R1S -N- R1S1CO-R31) - (V, b) - (r8-co) -r1s r15 <co-r8) .— 2o "(R« 'C0) ί ^' ΝγΝγΧ- R'15 -Χγ N - R15 iCO-R0) - ΝγΝ ΝγΝ (Vic) - (Re-COJj — R, s XX R1S (CO-R9) .— 25 R, 5 <CO-R8) - - (R »-C0): Η, ΓΧγγΧ- R'1S χγ nyn * r <s XCO-r8) - Nc ^ NN ^ N - (R9-CO) - r , 5— X n_Ri5_ (CO-R9) .- (Fld) 30 R15- (C0-R9) - '10121901 - (R' -CO): R15 Rti) <cO-Re) i— 5 - (FVCO): R, s - NN γΧ-R'ü-N R'ii X γ N γ N '^ - (CO-R.) - Li N ^ NN .N (Vie) I f if T [Z ^ N NR ^ CO-Rg) - ZR, 5 <C ° -Rb) - 10 vn, __ n-R'ii-X- ^ n xr ^ co-r ,,) - - (Re-CO): R16-X N..X R15. ^ ff Ί nLn γ Ϊ NtN (Vlf) - (Re-CO). · R | SI Λ XR «iC ° -Re) i" X ~ R ^ C ° -Re) '"Ri5 <c ° -Re) r 15 when s is 7, A is C7-C10 alkane heptayl; C7 -C12 alkane heptayl which is substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; or one of the groups with the formulas (Vila) - (Vlld) is 20 - (Re-c °) yr, 5 R1s (CO-Re) .— - (Re-CO) r R, s - N γΝ γΧ- R'15 -XNN - R15 - <CO-Re) - ΝγΝ ΝγΝ (R9-co) .— x n-r15- (CO-r9) - (Vila) R15- (CO-R9) - 25 - (R8- co) .r15 R, s (CO-r8) - \ / - (R.-CO): R1S - N γΝ γΧ-R '—- R'ii-X γ N γ N - R, 5- (CO- R8) - 30 ΝγΝ Ν 'N ΝγΝ (Vllb) Z z ^ N NR. ^ CO-Rg) - X-Rli- (CO-Re) r Ri5 <C0Re) - 1012190 μ_-R' --— - (RB -CO): Rlb-X'N ^ NV "XR> 5 I 15 10. C3-C10 alkane triyl; C3 -C12 alkane triyl which is substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; or one of the groups with the formulas (Ilia) - (llld) is r | q (Hla) 15 O I O. X Λ / Rex xrR, s R’ — χ2 K - (R8-CO) - R, s - X N X- R15iCO-R28) - 20 TT ΝγΝ (II lb) "(R9-CO) j R, 5 X - (Rg-CO) .— R15 25 - (Re-CO) r Rt5- N ^ X- Rl51CO-R28) - ΝγΝ I (MIC ) 1012190 rL, ζ γ (II id) _ X Λ 0 8 / ^ v'Y '^' R'6vX '^' r ^ Rg __ X, R9 if s is 4, A C4-C10 alkaneometry; C4-C12 alkanetetryl which is substituted with OH and / or is interrupted by oxygen, -NH- or -NR10-; or one of the groups of formulas (IVa) - (IVd) is X> 15. I 1 vV "rV Λ R29 20 - (RB-CO) r R1S- X ^ X- R'15 -χγ N γ X 'R <s ÏCO-RJ- ΝγΝ N ^ N (| Vb) - (Re -CO) .— r15— X x-r15- (C0-r9) - 25 - (Rg-COJj R, 5 - (Re-CO) Γ R, 5 - N _ N x- R, s fCO-R2e) - I II N ^ N 30 X-R15- (CO-R28) - (IVc) 1012190 '-. * - (R.-CO) - R1? R15 <CO-R <3> - \ / '- (Rg-CO) [R.-NyNyN-R, CO-R2e) - "NVN T <, vd) when s is 5, A C5 -C10 alkane pentayl; C5 -C12 alkane pentayl which is substituted with OH and / or interrupted by oxygen, -NH- or -NR] O-; or one of the groups of formulas 10 (Va) - (Vc) is RL-0 q q i y 15. Λ r \ y R m x X! V. "No ^ V> L I RA θ W29 20 R15 <CO-R8) - - (R.-CO) r R, s- X γΝ γ-Χ- R ', sX γ N γ N' BS-tCO-R.lr N <yN (Vb) - ( R9-CO) - R1S — XXR, s (cO-R9) j 25 - (Rg-CO) / R, s R <CO-R8) - \ / - (Re-CO): R, 5-NyNyN-R15 - (CO-R ,,,) - ΝγΝ \ (Vc) X-R) S- (CO-R28) - when s is 6, 1012190 A C6-C10 alkane hexayl; C 1 -C 8 alkane hexayl which is substituted with OH and / or interrupted by oxygen, -NH- or -NR10-; or one of the groups with the formulas (Via) - (Vlf) is 5 ο ^ γ ° O. X x Λ *. Λ, γΚ χ4 χγ * ^ <vla> ο ^ Χο ο A composition according to claim 9, which comprises 0.1 to 10% by weight, based on the material to be stabilized, of the stabilizer of component B. The composition of claim 9, further comprising a component selected from solvents, pigments, dyes, plasticizers, antioxidants, stabilizers, thixotropics, leveling aids, further light stabilizers, metal passivating agents, phosphites and phosphonites. A composition according to claim 12, which further comprises a light stabilizer from the class of the 2-hydroxyphenyl triazines and / or 2-hydroxyphenyl benzotriazoles. A method of stabilizing an organic material against damage from light, oxygen and / or heat, which comprises adding or applying to the material at least one compound of the formula Γ or II according to claim 5. 15. Use of a compound of the formula Γ or II according to claim 5 for stabilizing an organic material against damage by light, oxygen and / or heat. 1012190